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Institute of Physical Chemistry, Polish Academy of Sciences

SUPPORTING DOCUMENTATION FOR HABILITATION

APPLICATION(in English)

March 11, 2013

Piotr ZarzyckiInstitute of Physical Chemistry

Polish Academy of Sciences, Warsaw

Contents

1 Summary of professional accomplishments 31.1 Curriculum vitae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31.2 Scientific biography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2 Publications 72.1 Complete publications list . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72.2 Publications selected to support the habilitation application . . . . . . . . . . . . . . . . . . . . . . . 112.3 Publications: citation statistics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132.4 Description of the research presented in papers supporting habilitation application . . . . . . . . . . 14

2.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142.4.2 Research supporting habilitation application . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152.4.3 Accomplishments of research selected to support the habilitation application . . . . . . . . . 222.4.4 Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232.4.5 Future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3 Teaching, collaboration and science outreach activity 283.1 Teaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283.2 International collaboration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

3.2.1 Project: Metal oxide nanoparticles coated by organic ligands . . . . . . . . . . . . . . . . . . 283.2.2 Project: Non-equilibrium electrochemistry at the single-crystal electrode/electrolyte interface 283.2.3 Project: Protein pore (α-hemolysin) conductivity perturbations . . . . . . . . . . . . . . . . . 293.2.4 Project: Double electrical layer and charge transfer processes in bological systems . . . . . 293.2.5 Project: Non-innocent ligands in enzymatic charge transfer . . . . . . . . . . . . . . . . . . . 29

3.3 Science outreach acvity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303.3.1 Conference organizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303.3.2 Participation in domestic conferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303.3.3 Participation in international conferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Acknowledgements 32

2

Piotr Zarzycki, Habilitation application 3

1 Summary of professional accomplishments

1.1 Curriculum vitae

Name: Piotr Paweł ZarzyckiAddress: Institute Physical Chemistry

Polish Academy of SciencesKasprzaka 44/52, Warsaw 01-224

Education:2005 PhD in Physical Chemistry, Department of Theoretical Chemistry, Faculty of Chemistry,

Maria Curie-Skłodowska University, Lublinthesis ”Theoretical study of the equilibrium and kinetics of simple ions adsorption at the metal oxide/electrolyte interface” (advisor: dr. hab. Robert Charmas)

2002 Msc in Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Lublinthesis ”Simple theoretical model of proton adsorption isotherm derivativesobtained by using the high-resolution potentiometric titration”(advisor: prof. dr. hab. Władysław Rudziński)

Professional experience:2012 visiting scientist Department of Chemistry, Stanford University, California, US (E.I. Solomon)2012 visiting scientist Department of Chemistry, Cambridge University, UK (A. Whitley)2012 visiting scientist Chemical Biology, Department of Chemistry, Oxford University, UK (H. Bayley)2011- employed as an ”adiunkt” in the Institute of Physical Chemistry, PAS, Warsaw2008-2011 post-doctoral fellowship Pacific Northwest National Laboratory, Richland, Washington, US (K. Rosso)2007-2008 post-doctoral fellowship Department of Geology, University of California, Davis, US (J. Rustad)2006-2007 post-doctoral fellowship Department of Chemistry, University of California, Berkeley, US (D. Chandler)2005 visiting scientist Laboratoire Environnement et Mineralurgie, CRNS, Nancy, France (F. Thomas)2005-2008 employed in Institute of Catalysis and Surface Physicochemistry, PAS, Cracow2002 visiting scientist Laboratoire Environnement et Mineralurgie CRNS, Nancy, France (F. Villieras)

Awards:2012 FNP1 Mentoring 2012 laureate (collaboration with prof. H. Bayley from Oxford University, UK)2006 outgoing scholarship KOLUMB FNP1 (post-doctoral fellowship in UC Berkeley, US)2002 Certificate of Appreciation of the Chancellor of the Maria Curie-Skłodowska University

for the very good grades during the studies2002 award ”Primus Inter Pares” for one of the 15 best students in Poland in 20022002 award ”Primus Inter Pares” for the best student of the Lubelskie province in 20022002 award ”Primus Inter Pares” for the best student of Lublin city in 20022002 award ”Primus Inter Pares” for the best student of Maria Curie-Skłodowska University in 20022001-2002 Minister of National Education’s scholarship

Current research grants:2012-2015 NCN2 grant DEC-2011/03/B/ST5/02693: Electronic structure and electron transfer processes

in selected molecular prototypes with non-innocent ligands:Experimental and molecular modelling study (Primary investigator)

2011-2013 grant EU3 FP7-REGPOT-CT-2011-285949-NOBLESSE (employment in IPC PAS Warsaw)2011- ICM4 computational grants: G47-0 (Molecular Dynamics study of solvent effect on methyl vilogen

reduction potential) and G47-1 (Molecular dynamics of Shewanella oneidensis outermembrane)

Finished research grants:

1Foundation for Polish Science (pl. Fundacja Na Rzecz Nauki Polskiej)2National Science Center (pl. Narodowe Centrum Nauki)3European Union (pl. Unia Europejska)4Interdyscyplinarne Centrum Modelowania Matematycznego i Komputerowego, Uniwersytet Warszawski


2011-2012 FNP1 KOLUMB supporting grant2010-2011 Department of Energy USA (DOE), grant number: 39917

Coupled Surface and Solid-State Charge and Ion Transport Dynamics at Mineral/WaterInterfaces: Redox Transformation of the Iron Oxides (task: molecular modelling)

2007-2010 Department of Energy USA (DOE), grant number: 25629Reductive Transformation of Iron Oxides: Coupled Solution and Solid-State Pathways(task: molecular modelling)

Conference attendance5

Service experience:2002- reviewer of the internationally recognized journals: Journal of Colloid and Interface Science,

Langmuir, Journal of Physical Chemistry (A,B,C), Geochimica Cosmochimica Acta2006-2011 reviewer of the FNP1 grant applications

Co-curricular activities:1995-1998 member of the Polish National Olympic Team (in Taekwondo WTF); I represented Poland in

several international tournament; the most important was a participation in:World Junior Taekwondo Championship in Barcelona, Spain, June 27-30, 1996 (5th position)

1998 III position in Polish Championship in Taekwondo WTF, Gdańsk, May 17, 1998(bronze medal, weight class: -62 kg, age category: senior)

1996 I position in Polish Championship in Taekwondo WTF, 11th of November - 1st of December 1996, Śrem(gold medal, weight class: -66 kg, age category: kadet)

1995 I position in Polish Championship in Taekwondo WTF, Kętrzyn, November 18, 1995(gold medal, weight class: -66 kg, age category: kadet)

1995 II position in Poland Cup in Taekwondo WTF, Lublin, June 3, 1995(silver medal, weight class: -58 kg, age category: junior)

1995 II position in Poland Cup in Taekwondo WTF Lublin, June 3, 1995(silver medal, poomse, age category: junior)

1994 III position in Polish Championship in Taekwondo WTF (bronze medal, age category: kadet)1995 III position in Polish Youth Olympics in Taekwondo WTF, Wrocław, May 19-21, 19951994 III position in Polish Championship in Taekwondo WTF, Puławy, December 29, 1994

(bronze medal, weight clas: 54-58 kg, age category: kadet)

Warsaw, March 11, 2013

5Organization and participation in international conferences are presented in Section 3.3. Scientific outreach activity


1.2 Scientific biography

My scientific carrier had its beginning during my second year of studies at the Maria Curie-SklodowskaUniversity (Faculty of Chemistry),6 when I was included in the research projects conduced by dr. hab. RobertCharmas.7 Since the following year, I continued my studies according to the individual program, in which all majorcourses in Mathematics offered by the Department of Mathematics MCS University (lectures, classes and exams)were added to the regular study schedule prepared by the Faculty of Chemistry.

At that time, I embarked on several research projects led by dr. hab. Charmas, which typically involved theanalytical models of the electrical double layer formed at the metal oxide/electrolyte interface. Thanks to thecollaboration between dr. hab. Charmas and the Laboratoire Environnement et Minealurgie CNRS/INPL in Nancy,France (LEM-CNRS), I had an opportunity to work in an international research environment (i.e., collaboratingwith prof. Prelot,8 prof. Villieras,9 prof. Thomas8 and dr. hab. Piasecki10), as well as to work extensively abroad(LEM-CNRS).

After I graduated with honours in 2002 (MsC in Chemistry), I began the PhD studies at the Department ofTheoretical Chemistry, Faculty of Chemistry, MSC University under the supervision of dr. hab. Charmas. At thattime I started using the Monte Carlo method to simulate the metal oxide/electrolyte interface (with the help of dr.hab. Szabelski11), and the ab-inito method of calculating a charge distribution at the hydrated metal oxide surface(with the help of prof. Woliński10).

I had published several research papers, and defended my PhD in June 2005. In the same year, I was employedby the Institute of Catalysis and Surface Physicochemistry, Polish Academy of Sciences in Cracow, where I wasdeveloping and extending our Monte Carlo methods (including the ab-initio parametrization). I also started tolook for the post-doctoral position at the leading scientific institutions in the US.

In 2006, the Foundation for Polish Science granted me the post-doctoral fellowship (KOLUMB program) for ayear stay in David Chandler’s group at the University of California, Berkeley (US). That year I spent on an intenselearning of molecular modelling methods, developing my own parallel simulation codes, including: moleculardynamics, ab-initio dynamics, and algorithms designed for calculating free energy of chemical transformation (e.g.,Umbrella Sampling). I participated in several courses offered by the Department of Chemistry and Department ofPhysics (UC Berkeley), which have a huge impact on my further work. The Advanced Statistical Mechanics (prof.Gaissler, summer semester, 2007) and Advanced Quantum Mechanics (prof. Miller, summer semester, 2007) wereamong the most influential ones. Having been a member of Chandler’s group, gave me a unique opportunity to learnfrom his talented co-workers including: Thomas Miller,12 Adam Willard,13 Yael Elmatad,14 or Hans Andersen.15

My next goal was to apply the skills gained in Chandler’s group to my study of the metal oxide/electrolytesolution interface. For that reason, I joined prof. James Rustad’s16 group at the Department of Geology, University ofCalifornia, Davis (US) in 2007 (i.e., my second post-doctoral fellowship). Prof. Rustad is a world-wide recognizedleader in the molecular geochemistry. In my research done under prof. Rustad’s supervision I combined themolecular dynamics methods with ab-initio calculations in order to calculate the NMR spectra of homogeneousliquid phases (e.g., ethanol). I also used the ab-initio molecular dynamics (Car-Parrinello) along with the staticfrequency calculations to study the isotopic effects in minerals. In the following year, encouraged by prof. Rustad,I went through the several recruitment steps to get a fellowship position at the Pacific Northwest NationalLaboratory w Richland (Washington, US) in prof. Kevin Rosso’s17 group. I was employed in PNNL in September2008. In prof. Rosso’s group I studied the charge transfer processes in both prototypical systems and at the

6at that time, the adsorption of gases and liquids on the solid surfaces was the main research theme in the Faculty of Chemistry, MCSUniversity. For decades, the so-called the ”Lublin Surface Science School” has been established. Some of the most influential figureswere/are: J. Ościk, R. Szczypa, A. Dąbrowski, W. Rudziński, E. and S. Chibowski, M. Jaroniec, W. Janusz, M. Kosmulski, J. Jagiełło, T.Borowiecki, T. Pańczyk, R. Leboda, J. Goworek, P. Szabelski, R. Charmas, S. Sokołowski, M. Borówko, A. Patrykiejew, P. Bryk (and manyothers...)

7currently: the Dean of the State Higher School of Computer Science and Business Administration in Łomża8currently: Institut Charles Gerhard Montpellier CNRS, Universite Montpellier II, Montpellier, France9currently: Laboratoire Environnement et Mineralurgie, CNRS/INPL, Vandoeuvre-les-Nancy Cedex, France

10Biochemistry Department, AWF Warsaw11Department of Theoretical Chemistry, MSC University12currently: Department of Chemistry, California Institute of Technology, Pasadena, California13currently: Department of Chemistry and Biochemistry, University of Texas, at Austin14currently: Center for Soft Matter Research, Department of Physics, New York University, NY15currently: Department of Chemistry, Stanford University, Stanford, CA16currently: Science and Technology Division, Corning, Inc., Corning, NY17currently: Associate Director, Geochemistry, Fundamental and Computational Sciences Directorate, Chemical and Material Sciences

Division, Environmental Dynamics and Simulation, Pacific Northwest National Laboratory, Richland, WA


metal oxide/electrolyte interface. My collaboration with an experimental part of prof. Rosso’s group enabledme to develop a new method of analyzing electrochemical measurements involving the single-crystal electrode(in our case α-Fe2O3) that selectively exposes only a single-crystal face to the electrolyte solution. In 2010,with the help of prof. Rosso, I started a collaboration with prof. Blumberger’s18 and prof. Richardson’s19 groups.In that research project, I used the molecular dynamics to model the electronic conductance of the deca-hemecytochrome isolated from Gram-negative bacteria Shewanella Oneidensis MR-1. It was the first project, in which Iused molecular modelling methods (molecular dynamics, pH-dependent Monte Carlo, and ab-initio calculations ofelectronic coupling in electron transfer processes between heme-cofactors) to a large biological system.20 This workinitiated my further interest in the electrochemical processes (including charge transfer) in biologically relevantsystems. I also co-organized with prof. Rosso the microsymposium entitled Electron Transfer at Mineral Surfacesand Biogeochemical Implications during the 242nd ACS National Meeting & Exposition held in Denver, ColoradoUS (28th of August to 1st of September, 2011).21

In 2010, with the help of prof. Rosso I started a collaboration with prof. Gilbert.22 During my work in this multi-team collaborative project, I developed a new coarse-grained lattice Monte Carlo simulation model to interpretexperimental work carried out in prof. Gilbert’s group. The simulations were used to trace the fate of a smallpolaron formed inside the metal oxide nanoparticles, in particular its slow thermally-limited diffusion (hopping).The subject of those two last collaborative projects is the main theme of my on-going research activity at thismoment.

Due to the family circumstances I returned to Poland in October 2011, where I was employed at the Instituteof Physical Chemistry, Polish Academy of Sciences in Warsaw. I joined prof. Lewinski’s group,23 where I have beenworking on my own research projects (see Section 3.2) and I have been supporting experimental studies beingconducted by prof. Lewiński’s group. I am also continuing my collaboration with prof. Rosso and his co-workers.24

In 2012, I started a collaboration with prof. Solomon’s group from the Department of Chemistry, Stanford Uni-versity, US. Our collaborative research project is directly related to realization of the NCN grant.25 Specifically, weare looking at the ligands participation in an enzymatic charge transfer in aPHM (peptidylglycine α-hydroxylatingmonooxygenase). In 2012, FNP granted me the Mentoring fellowship for the collaboration with prof. Bayley fromthe Department of Chemical Biology, Oxford University (UK). In this research project, I have been using molecularmodelling to understand the electronic conductance and reactivity of single molecules in protein pore formed bybacterial toxin α-hemolysin of Staphylococcus aureus. Details of my current work-in-progress can be found inSection 3.2 International collaboration.

I have selected 16 publications to support my habilitation application. In all papers I am either the sole authoror the major contributor.26 What is more, in all chosen papers, I am the first author and the only correspondingauthor. They summarise my over eight year effort to understand the acid-base properties of the mineral surface onthe molecular level, consolidation those findings with the available experiments and developing new mathematicaltools for interpreting new experimental data.


18currently: University College London, Department of Physics and Astronomy, London, UK19currently: Microbial Biochemistry, University of East Anglia, Norwich, UK20approximately 106 atoms in a primary computational cell21details may be found in Section 3.3. Science outreach activity22currently: Lawrence Berkeley National Laboratory, Berkeley, US23who works both in Institute of Physical Chemistry, PAS and in Faculty of Chemistry, Technical University of Warsaw24all on-going research projects are described in Section 3.2 International collaboration25NCN DEC-2011/03/B/ST5/0269326as confirmed by the co-authors declaration, see the attachment (d)


2 Publications

2.1 Complete publications list

The complete list of the research papers published after obtaining the MsC degree in 2002 (presented in areversed chronological order). Publications selected to support the habilitation application are in blue.27 Publi-cations in the highest impact factor journals are in brown.

2013 IF28

P1 S. Chatman, P. Zarzycki, T. Preocanin, K. M. RossoEffect of Surface Site Interactions on Potentiometric Titration of Hematite (α-Fe2O3) Crystal Faces.Journal of Colloid and Interface Science (2013) 391, 125-134. 3.07My contribution is about 30%: I prepared molecular models of a few crystal faces of hematite.I provided theoretical interpretation of experimental data based on my concept ofelectrostatic trapping of surface-bound protons. I wrote the theoretical description and coedited manuscript.

2012

P2 M. Breuer, P. Zarzycki, L. Shi, T. A. Clarke, M. J. Edwards, J. N. Butt, D. J. Richardson,J. K. Fredrickson, J. M. Zachara, J. Blumberger K. M. RossoMolecular structure and free energy landscape for electron transport in the decahaem cytochrome MtrFBiochemical Society Transactions (2012) 40, 1198-1203 3.71My contribution is about 25%: I developed molecular models and provided the results of electrontransfer free energy (between the heme cofactors in cytochrome). I was involved in manuscript writing.

P3 J. E. Katz, X. Zhang, K. Attenkofer, K. W. Chapman, C. Frandsen, P. Zarzycki, K. M. Rosso, R. W. Falcone,G. A. Waychunas, B. Gilbert,Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide NanoparticlesScience 337 (2012) 1200-1203 31.02My contribution is about 10%: I developed the lattice Monte Carlo models of polaron formingand hopping, QM calculations of polaron formation. I prepared the theoreticaldescription for the main manuscript and the accompanying Supporting Materials.

P4 M. Breuer, P. Zarzycki, J. Blumberger, K.M. RossoThermodynamics of electron flow in the bacterial deca-heme cytochrome MtrFJournal of the American Chemical Society 134 (2012) 9868 -9871 9.91My contribution is about 40%: I developed molecular models, ran molecular dynamics simulations of electrontransfer free energy. I analysed results, wrote the first draft of manuscript.

P5 P. Zarzycki, T. PreocaninPoint of zero potential of single-crystal electrode/inert electrolyte interfaceJournal of Colloid and Interface Science 370 (2012) 139-143 3.07My contribution is about 80%: I designed the research, analysed available experimental data and wrote manuscript.

2011

P6 P. Zarzycki, S. Kerisit, K. M. RossoComputational methods for intramolecular electron transfer in a ferrous-ferric iron complexJournal of Colloid and Interface Science 361 (2011) 293-306 3.07My contribution is about 80%: I designed the research, I carried out all calculations, analysed resultsand wrote manuscript.

P7 P. Zarzycki, S. Chatman, T. Preocanin, K. M. RossoElectrostatic potential of specific mineral facesLangmuir 27 (2011) 7986-7990 4.19My contribution is about 70%: I designed the research, delveloped the mathematical model for analysingpotentiometric titration exhibiting hysteretic loops, developed the user-friendly software, analysedexperimental data (obtained by S. Chatman), wrote manuscript and Supporting Materials(except the technical description of experimental setup, which was written by S. Chatman).

27these papers are repeated in the next section28current Impact Factor of a given journal according to the Journal Citation Reports® (Web of Knowledge, Thomson Reuters, 2011)


2010

P8 P. Zarzycki, K. M. Rosso, S. Chatman, T. Preocanin, N. Kallay, W. PiaseckiTheory, experiment and computer simulation of the electrostatic potential at crystal/electrolyte interfacesCroatica Chemica Acta 83 (2010) 457-474 (Invited Feature Article) 0.76My contribution is about 80% (this is a review paper): I designed the paper, derived all equationsand wrote the manuscript.

P9 P. Zarzycki, K. M. RossoMolecular Dynamics of the AgCl/Electrolyte Interfacial CapacityJournal of Physical Chemistry C 114 (2010) 10019-10026 4.81My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

P10 P. Zarzycki, S. Kerisit, K. M. RossoMolecular Dynamics Study of the Electrical Double Layer at Silver Chloride-Electrolyte Interfaces

Journal of Physical Chemistry C 114 (2010) 8905-8916 4.81My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

P11 P. Zarzycki, K. M. RossoNonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces.A Monte Carlo simulation studyJournal of Colloid and Interface Science 341 (2010) 143-152 3.07My contribution is about 80%: I designed the paper, carried out all calculations, and derived all equations.I analysed results and wrote the manuscript.

P12 W. Piasecki, P. Zarzycki, R. CharmasAdsorption of alkali metal cations and halide anions on metal oxides: prediction of Hofmeister seriesusing 1-pK triple layer model.

Adsorption 16 (2010) 295-303 2.0My contribution is about 5%: I re-edited the manuscript.

2009

P13 P. Zarzycki, K. M. RossoOrigin of Two Time-Scale Regimes in Potentiometric Titration of Metal Oxides.A Replica Kinetic Monte Carlo StudyLangmuir 25 (2009) 6841-6848 4.19My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

P14 P. Zarzycki, J. R. RustadTheoretical Determination of the NMR Spectrum of Liquid EthanolJournal of Physical Chemistry A 113 (2009) 291-297 2.95My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

2008

P15 J. R. Rustad, P. ZarzyckiCalculation of site-specific carbon-isotope fractionation in pedogenic oxide mineralsProceedings of the National Academy of Sciences of the USA 105 (2008) 10297-10301 9.68My contribution is about 40%: I ran some of presented calculations and prepared the results for publication.

2007

P16 P. ZarzyckiComputational Study of Proton Binding at the Rutile/Electrolyte Solution InterfaceJournal of Physical Chemistry C 111 (2007) 7692-7703 4.81My contribution is about 100%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

P17 P. ZarzyckiComparison of the Monte Carlo estimation of surface electrostatic potentialat the hematite (0001)/electrolyte interface with the experimentApplied Surface Science 253 (2007) 7604-7612 2.1My contribution is about 100%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

P18 P. ZarzyckiEffective adsorption energy distribution function as a new mean-fieldcharacteristic of surface heterogeneity in adsorption systems with lateral interactionsJournal of Colloid and Interface Science 311 (2007) 622-627 3.07My contribution is about 100%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.


P19 P. ZarzyckiMonte Carlo modelling of ion adsorption at the energetically heterogeneousmetal oxide/electrolyte interface: Micro- and macroscopic correlations between adsorption energies

Journal of Colloid and Interface Science 306 (2007) 328-336 3.07My contribution is about 100%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.

P20 P. ZarzyckiKinetic Monte Carlo study of proton binding at the metal oxide/electrolyte interfaceJournal of Colloid and Interface Science 315 (2007) 54-62 3.07My contribution is about 100%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.

P21 P. Zarzycki, P. Szabelski, W. PiaseckiModelling of ζ-potential of the montmorillonite/electrolyte solution interfaceApplied Surface Science 253 (2007) 5791-5796 2.1My contribution is about 80%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.

P22 W. Piasecki, P. Zarzycki, W. RudzińskiRelaxation time of proton adsorption from solution onto magnetite and anatase:Classical and new theoretical approachCroatica Chemica Acta 80 (2007) 345-349 0.76My contribution is about 5%: I edited the manuscript.

2006

P23 P. ZarzyckiMonte Carlo Study of the Topographic Effects on the Proton Binding at the Energetically HeterogeneousMetal Oxide/Electrolyte InterfaceLangmuir 22 (2006) 11234-11240 4.19My contribution is about 100%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.

P24 P. ZarzyckiMonte Carlo simulation of the electrical differential capacitance of adouble electrical layer formed at the heterogeneous metal oxide/electrolyte interfaceJournal of Colloid Interface Science 297 (2006) 204-214 3.07My contribution is about 100%: I designed the paper, ran all calculations, analysed results, wrote the manuscript.

P25 P. Zarzycki, F. ThomasTheoretical study of the acid-base properties of the montmorillonite/electrolyte interface:Influence of the surface heterogeneity and ionic strength on the potentiometric titration curvesJournal of Colloid Interface Science 302 (2006) 547-559 3.07My contribution is about 80%: I derived all equations, ran calculations, analysed results, wrote the manuscript.

Publications before PhD2005

P26 P. Zarzycki, P. Szabelski, R. CharmasRole of the surface heterogeneity in adsorption of hydrogen ions on metal oxides:Theory and simulationsJournal of Computational Chemistry 26 (2005) 1079-1088. 4.58My contribution is about 60%: I ran calculations, analysed results, we wrote the manuscript together.

P27 P. Zarzycki, P. Szabelski, R. CharmasA Monte Carlo simulation of the heterogeneous adsorption of hydrogen ions onmetal oxides: Effect of inert electrolyteApplied Surface Science 252 (2005) 752-758. 2.1My contribution is about 60%: I ran calculations, analysed results, we wrote the manuscript together.

2004

P28 P. Zarzycki, R. Charmas, P. SzabelskiStudy of proton adsorption at heterogeneous oxide/electrolyte interface:Prediction of the surface potential using Monte Carlo simulations and 1-pK approachJournal of Computational Chemistry 25 (2004) 704-711. 4.58My contribution is about 60%: I ran calculations, analysed results, we wrote the manuscript together.

P29 P. Zarzycki, R. Charmas, W. PiaseckiFormal Mathematical Analysis of the Existence of the Common Intersection Point inRelation to Determining the Parameters Describing Ion Adsorption at the Oxide/ElectrolyteInterface: Comparison of the Triple and Four-Layer ModelsAdsorption 10 (2004) 139-149 2.0My contribution is about 20%: I ran calculations and developed some codes under prof. Charmas’ supervision.

P30 P. Szabelski P. Zarzycki, R. CharmasMonte Carlo Study of Proton Adsorption at the Heterogeneous Oxide/ Electrolyte Interface

Langmuir 20 (2004) 997-1002 4.19My contribution is about 30%: I ran calculations and developed some codes under prof. Szabelski’s supervision.


P31 R. Charmas, P. Zarzycki, F. Villieras, F. Thomas, B. Prelot, W. PiaseckiInfluence of electrolyte ion adsorption on the derivative of potentiometric titration curveof oxide suspension - theoretical analysisColloids and Surfaces. A-Physicochemical and Engineering Aspects 244 (2004) 9-17 2.24My contribution is about 10%: I ran calculations and developed some codes under prof. Charmas’ supervision.

2002

P32 B. Prelot, R. Charmas, P. Zarzycki, F. Thomas, F. Villieras, W. Piasecki, W. RudzinskiApplication of the Theoretical 1-pK Approach to Analysing Proton Adsorption IsothermDerivatives on Heterogeneous Oxide Surfaces.Journal of Physical Chemistry B 106 (2002) 13280-13286 3.7My contribution is about 10%: I ran calculations and developed some codes under prof. Charmas’ supervision.


2.2 Publications selected to support the habilitation application

# Article29 IF28 %30 Nc31

H1 P. Zarzycki, F. ThomasTheoretical study of the acid-base properties of the montmorillonite/electrolyte interface:Influence of the surface heterogeneity and ionic strength on the potentiometric titration curvesJournal of Colloid Interface Science 302 (2006) 547-559 3.07 80% 12My contribution is about 80%: I derived all equations, ran calculations, analysed results,wrote the manuscript.

H2 P. ZarzyckiMonte Carlo modelling of ion adsorption at the energetically heterogeneousmetal oxide/electrolyte interface: Micro- and macroscopic correlations between adsorption energies

Journal of Colloid and Interface Science 306 (2007) 328-336 3.07 100% 6My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H3 P. ZarzyckiMonte Carlo Study of the Topographic Effects on the Proton Binding at the EnergeticallyHeterogeneous Metal Oxide/Electrolyte InterfaceLangmuir 22 (2006) 11234-11240 4.19 100% 7My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H4 P. ZarzyckiEffective adsorption energy distribution function as a new mean-fieldcharacteristic of surface heterogeneity in adsorption systems with lateral interactionsJournal of Colloid and Interface Science 311 (2007) 622-627 3.07 100% 3My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H5 P. ZarzyckiMonte Carlo simulation of the electrical differential capacitance of adouble electrical layer formed at the heterogeneous metal oxide/electrolyte interfaceJournal of Colloid Interface Science 297 (2006) 204-214 3.07 100% 9My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H6 P. ZarzyckiComputational Study of Proton Binding at the Rutile/Electrolyte Solution InterfaceJournal of Physical Chemistry C 111 (2007) 7692-7703 4.81 100% 4My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H7 P. ZarzyckiKinetic Monte Carlo study of proton binding at the metal oxide/electrolyte interfaceJournal of Colloid and Interface Science 315 (2007) 54-62 3.07 100% 3My contribution equals 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

H8 P. Zarzycki, K. M. RossoOrigin of Two Time-Scale Regimes in Potentiometric Titration of Metal Oxides.A Replica Kinetic Monte Carlo StudyLangmuir 25 (2009) 6841-6848 4.19 80% 7My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

H9 P. ZarzyckiComparison of the Monte Carlo estimation of surface electrostatic potentialat the hematite (0001)/electrolyte interface with the experimentApplied Surface Science 253 (2007) 7604-7612 2.1 100% 8My contribution is about 100%: I designed the paper, ran all calculations, analysed results,wrote the manuscript.

29I have selected 16 papers in which I am the first and corresponding author. They form a comprehensive sequence of research articlesin the theme of electrostatic properties of the double electrical layer formed at the mineral/electrolyte interface.

30my estimated contribution in article in %31number of all citing articles according to the Web of Knowledge (Thomson Reuters, 2011) on February 22nd , 2013


# Article29 IF28 %30 Nc31

H10 P. Zarzycki, K. M. RossoNonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces.A Monte Carlo simulation studyJournal of Colloid and Interface Science 341 (2010) 143-152 3.07 80% 6My contribution is about 80%: I designed the paper, carried out all calculations, and derived all equations.I analysed results and wrote the manuscript.

H11 P. Zarzycki, K. M. Rosso, S. Chatman, T. Preocanin, N. Kallay, W. PiaseckiTheory, experiment and computer simulation of the electrostatic potential at crystal/electrolyte interfacesCroatica Chemica Acta 83 (2010) 457-474 (Invited Feature Article) 0.76 80% 2My contribution is about 80% (this is a review paper): I designed the paper, derived all equationsand wrote the manuscript.

H12 P. Zarzycki, S. Chatman, T. Preocanin, K. M. RossoElectrostatic potential of specific mineral facesLangmuir 27 (2011) 7986-7990 4.19 70% 3My contribution is about 70%: I designed the research, delveloped the mathematical model for analysingpotentiometric titration exhibiting hysteretic loops, developed the user-friendly software, analysedexperimental data (obtained by S. Chatman), wrote manuscript and Supporting Materials(except the technical description of experimental setup, which was written by S. Chatman).

H13 P. Zarzycki, T. PreocaninPoint of zero potential of single-crystal electrode/inert electrolyte interfaceJournal of Colloid and Interface Science 370 (2012) 139-143 3.07 80% 0My contribution is about 80%: I designed the research, analysed available experimental data.I wrote the manuscript.

H14 P. Zarzycki, S. Kerisit, K. M. RossoMolecular Dynamics Study of the Electrical Double Layer at Silver Chloride-Electrolyte Interfaces

Journal of Physical Chemistry C 114 (2010) 8905-8916 4.81 80% 10My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

H15 P. Zarzycki, K. M. RossoMolecular Dynamics of the AgCl/Electrolyte Interfacial CapacityJournal of Physical Chemistry C 114 (2010) 10019-10026 4.81 80% 7My contribution is about 80%: I designed the paper, carried out all calculations, analysed resultsand wrote the manuscript.

H16 P. Zarzycki, S. Kerisit, K. M. RossoComputational methods for intramolecular electron transfer in a ferrous-ferric iron complexJournal of Colloid and Interface Science 361 (2011) 293-306 3.07 80% 0My contribution is about 80%: I designed the research, I carried out all calculations, analysed resultsand wrote the manuscript.


2.3 Publications: citation statistics

• Summary of the all publications32 (Section 2.1):Publications 32Sum of publications Impact Factor 142Sum of the times cited 185Sum of the times cited without self-citations 90Citing articles 95Citing articles without self-citations 73Average citations per item 5.78H-index: 8

• Summary of the articles selected to support the habilitation application32 (Section 2.2):Publications 16Sum of publications Impact Factor 54.4Sum of the times cited 87Sum of the times cited without self-citations 45Sum of the times cite 47Citing articles without self-citations 34Average citations per item 5.44H-index: 7

32statistics generated by the Web of Knowledge (Thomson Reuters, 2011) on February 22nd , 2013; except the Sum of publicationsImpact Factor which is the sum of the publications Impact Factor from the lists in Sections 2.1 i 2.2.


2.4 Description of the research presented in papers supporting habilitation application

2.4.1 Introduction

c1

SOH A-(1-z)+

2

SOH A-(1-z)+

2

SOH C+z-

SOH C+z-

-

+

+

y0

yb

yd

sb

sd

s0

c

y0 yb

b0

SOH A-(1-z)+

2

met

al o

xide

C+

SOHz-

SOH(1-z)+2

SOHz-

1

s0

c2

z

(a)

(b)

(c)

-

l

Figure 1: Electrical double layer at the metaloxide/electrolyte interface: a) molecular rep-resentation used in simulation study, b) sto-ichiometry and structure of the surface com-plexes, c) reduction to the layer (conceptual)model used in analytical modelling (see pa-per [H11])

The key environmental and biological processes (dissolution, mineralformations and transformations, red-ox and heavy/radioactive ions accumu-lation) take place at the mineral/electrolyte interface [1, 2, 3, 4, 5, 6].

If minerals are brought into contact with an aqueous phase, the excesscharge is generated on its surface. The dissociation of the surface groupsand molecular/dissociative water sorption are the primary sources of thissurface charge [2, 3], which is consequently compensated by the electrolyteions accumulated near the surface. The spacial charge distribution formedin such a way is called the electrical double layer (e.d.l.) [6, 7, 8]. Dueto the fact, that surface charge is primarily determined by the proton up-take/release by the surface groups33, the H+ ions are commonly refereed toas the potential determining ions.34 As a result, the electrostatic propertiesof e.d.l. are typically presented as the function of pH. The surface chargedensity (σ0=f(pH)), surface potential (ψ0=f(pH)) and electrokinetic poten-tial (ζ=f(pH)) are among the most frequently reported ones. It is believedthat those properties are continuous and monotonic functions of pH [3, 5].They also posses a characteristic zero-value point at a specific pH value,which is called: Point of Zero Charge (PZC, in the case of σ0), Point ofZero Potential (PZP, in the case of ψ0) and isoelectric point (IEP, in thecase of ζ).35 If there is a lack of specific ions adsorption36 and the perma-nent isomorphic structural charge, then all three points (PZC, PZP, IEP)intersect [12, 3, 10, 11].

Besides that each of the characteristics mentioned above (σ0, ψ0, ζ) pro-vides a similar insight into the e.d.l.; the potentiometric titration of the metaloxide suspension (σ0, PZC) and electrokinetic measurements (ζ , IEP) arethe most frequently reported descriptors. Whereas the surface potential issill posing a noticeable experimental challenge (see [H11]).

The PZC and IEP values are considered as convenient, qualitative de-scriptors of the acid-base property of the metal oxide/electrolyte interface,and for this reason they are often used in comparative analysis and in mod-eling of the e.d.l. formed at the mineral/electrolyte interface [13, 14, 15].

The theoretical modelling of the discussed interface requires an assump-tion of the surface protonation mechanism (e.g., 1-pK [16], 2-pK [17], MU-SIC [18]) and a postulate of the charge spacial distribution (i.e., Helmholtz,Gouy-Champan or Stern e.d.l. model) [6, 7, 8]. The theoretical descrip-tion constructed in such a way is called the Surface Complexation Model(SCM) [3, 4, 5]. Surface proton uptake/release and electrolyte ions sorptionprocesses are considered as the electro-chemical reactions with a well-defined (apparent) equilibrium constants (Ki)37, in whose definition thesurface ionic concentrations are calculated from the bulk ones by includingthe electrostatic weighting factor.38 From now on, these theoretical modelswill be called the analytical ones (Fig. 1).39

33as well as the OH− ions34abbreviation: PDI35the more elaborate nomenclature was proposed by Sposito [9, 10, 11]36electrolyte ions near the surface have an unperturbed first hydration sphere, that is, they form outer-sphere complexes37one can also distinguish an intrinsic equilibrium constant, which is independent of σ0 and ψ0

38e.g., for H+ ions we have [H+]surf = [H+]bulk exp (−eψ0/kBT )39mathematical abstract models in which expressions for the macroscopically observables are derived using statistical mechanics and the

assumed nature and stoichiometry of the surface reactions. Those equations are typically used to interpret experimental data by discussingthe values of their best-fit parameters.


All papers, which has been selected to support my habilitation application (Section 2.2), are devoted to studyof electrostatic properties of the e.d.l. formed at the mineral/electrolyte solution interface. These publications arethe records of my over eight year effort to understand processes occurring at the charged semiconductor (insulator)/electrolyte interface on the molecular level. In particular, I was looking into the rationale (physical justification) ofseveral ad-hoc assumptions typically involved in analytical model construction. I was able to estimate the valuesof a few properties, which are experimentally inaccessible. In my work I mainly used the lattice models, which areinspired by Borkovec et al. [19, 20, 21, 22, 23] (Fig. 1), and which I had started developing earlier during my PhDstudies.

The research problems considered in those papers (Section 2.2) include: (1) application of the Surface Com-plexation Models to the clay systems ([H1]), (2) effect of the topological and energetic correlations on the ionssurface-binding events ([H2, H3]), (3) long-range (electrostatic) screening effects ([H3, H4]), (7) capacity and di-electric constant of the surface water layers ([H5, H15]), (4) molecular/dissociative mechanism of water sorptionon metal oxide surface ([H6]), (5) non-linearity of surface potential and kinetic dichotomy in proton uptake bythe mineral surface ([H7, H8, H10]), (6) determining an electrostatic potential (and PZC) of the isolated mineralcrystal faces ([H9, H11, H12, H13]), (8) adsorption free energy ([H14]), (9) inner/outer-sphere complex formation,coordinational preference and presence of energetic barriers along the ion adsorption pathway ([H14]), (10) elec-tron transfer, with a special focus on the isotopic effects, entropic and enthalpic contributions to the overall chargetransfer energetics ([H16]).

2.4.2 Research supporting habilitation application

x

y

e(x,y)

P( )e

eFigure 2: Reduced, statisti-cal (averaged) representation ofthe surface energetic hetero-geneity: ǫ(x, y) 7→ P (ǫ)

In my work I was using the SCM models developed by Rudziński, Charmas, Pi-asecki and coworkers [24, 25, 26, 27] to analyse experimental data [H1], as well asthe computer simulation results (treated as the computer experiments) [H2, H4]. Theunique feature of the analytical models developed in Charmas’ group [24, 25, 26, 27] isthe description of energetic surface heterogeneity within the framework of the IntegralAdsorption Isotherm (IAI) [28, 29, 30, 31, 32].

The key element of IAI is a statistical description of the surface heterogeneitywhich employs the adsorption energy probability distribution function.40 The actualmetal oxide surface is energetically non-uniform due to the several phenomena; themost relevant processes are: surface/subsurface reconstruction and relaxation, defects,stoichiometric perturbations and the isomorphic substitutions [10, 11, 24, 25, 26, 27].

Unfortunately, if the stochastic description provided by the IAI theory is used, thenall information about spacial non-uniformity, topological and local correlation effectsare lost at the expense of an average one-dimensional probabilistic function (Fig. 2).In a few papers described bellow [H2, H3, H8, H10] I used Monte Carlo simulations tostudy the energetic heterogeneity effects, which are inaccessible using the IAI theory. Those publications representthe continuation of my previous research (before PhD), and they were published during my first year of work inthe Institute of Catalysis and Surface Physicochemistry PAS in Cracow.41.

HO-Si

HO-Al

HO-Si

X-C

exc

X-C

exc

X-C

exc

X-C

exc

X-C

exc

HO-Si

HO-Al

HO-Si

X-C

exc

X-C

exc

X-C

exc

X-C

exc

X-C

exc

C = Na ,K , Ca+ + +2

1/2exc

Figure 3: Montmorillonite crystal [H1]

In one of my first papers published after obtained PhD (re-search done during my stay in prof. Thomas’ group42), I showedhow the simple SCM model that takes into account the surfaceenergetic non-uniformity, can explain available experimental po-tentiometric titration data for the clay systems (montmorillonite).An interesting feature of the montmorillonite/electrolyte interfaceis the parallelism of the potentiometric titration curves for var-ious ionic strength. The parallelism of the titration curves is aconsequence of the presence of permanent charge resulting fromthe isomorphic substitutions in the clay structure. Montmoril-lonite crystal has a disc-shape morphology with an exchangeablecations Na+ on the basal plane and protonable groups ≡AlO,

≡SiO (typical for metal oxide) on the edges [10, 11] (Fig. 3). By assuming the Gaussian distribution of the

40in our case, proton/ion affinity distribution function, P (pKi)412005-2006, before starting my post-doctoral fellowship; papers were finally in press in 200742Laboratoire Environnement et Mineralurgie, CNRS/INPL, Vandoeuvre-les-Nancy Cedex, France


adsorption/exchange energy, we were able to recreate the parallel titration curves for a realistic range of ionicexchange constant.

SOH2

SOH

da

ew=80

es=3

C

B

A

Figure 4: Lattice model of the metal oxide/electrolyteinterface used in simulations [H2, H3, H4, H5, H7, H8,H10]

In the case of non-specific ion sorption, the formation of surfacecomplexes is governed by the electrostatic attraction. This sug-gests, that the distributions of ion sorption energies are most likelycoupled. Assuming that adsorption energy distributions may besufficiently well described using the Gaussian function, the pres-ence of those correlations manifest themselves in a relative shift ofadsorption energy maxima (average energies), while the functionshapes are conserved [24]. By including such macroscopic ener-getic correlations in lattice model used in Monte Carlo simulations(Fig. 4), I showed how in a relatively simple way, the distinct ex-perimental situations may be recreated by changing only an extentof the distribution correlation.

It seems to be obvious that the local environment of a givenadsorption site i, (presence of the electrolyte ions, protonationstate of surrounding sites) affects the sorption/protonation affinityof this site (Fig. 5). What is more, electrostatic interactions arecable of propagating some configurational correlation on large distances (via the long-range electrostatic coupling).Unfortunately, all kinds of topological correlations are difficult to be described in a statistical manner, and for thisreason they are often neglected within the IAI framework.

-10

0

10

20

30

pKa

-10

0

10

20

30

pKb

0

0.05

0.1

0.15

0.2

G2

0

10

20pKa

0 5 10 15 20

0

5

10

15

20

pKA

pKC

pKC

pKA

adsorption

center

adsorption

center

saddle

point

adsorption

center

saddle point

(b)

(a)

Figure 5: Macro- and micro-scopic correlation between elec-trolyte ions affinities pKi (a), andlocal site correlations (b) (figurestaken from papers [H2, H3])

In paper [H3], I showed how the topological correlations affect the macroscopicobservable (e.g., σ0). If the long-range electrostatic interactions are neglect, weobserve the step-wise adsorption/protonation isotherms, which are similar to theisotherms of physisorpting gases on the patch-wise or porous surfaces. However, ifelectrostatic interactions are taken into account, the step-wise character is smearedout. In other words, the long-range electrostatic correlations screen (smooth) thelocal topological surface defects. This observation suggests that both electrostaticinteractions and local energetic heterogeneity do not need to be separated in atheoretical description, and the more accurate IAI approach within the framework ofthe Mean Field Approximation may be obtained if the surface energetics is describedin an unified way. In paper [H4], we proposed to use the pH-dependent energydistribution function which describes both local (chemical, van der Waals energetics)and the long-range electrostatics.

One of the commonly used approximation used in constructing the SCM theoryis based on the plane capacitor model43 (Fig. 6). This approximation imposes theconstant value of capacity, which in turn does not seem to be physically justified ifthe strong pH-dependence of surface potential and charge are taken into account.What is more, in many cases the SCM fitting of experimental data requires at leasttwo different capacity values (one for pH<PZC and another for pH>PZC) (see forinstance ref. [27]). On the other hand, there are several theoretical reports showinga strong functional dependence of e.d.l. capacity on temperature, ionic strength andother macroscopic parameters [33, 34, 35, 36, 37, 38, 39]. More specifically, thepresence of extreme capacity value near PZC was reported [33, 34, 35, 36, 37, 38,39] . The extreme capacity value as a function of temperature or ionic strengthmay be considered as an indirect evidence for the phase transitions (e.g., orderingtransformations of the monolayer or subsurface atoms). In my work published in2006 [H5] I showed how the differential capacity (cd) of the e.d.l. formed at themetal oxide/electrolyte interface can be directly estimated from the Monte Carlosimulations based on the following mathematical transformation:

cd =∂σ0∂ψ0

=∂σ0∂pH

∂f−1(ψ0)

ψ0(1)

My simulations [H5] proved that the electrical capacity possesses an extreme value near PZC also in the case of

43or series of plane capacitors connected in parallel


the metal oxide/electrolyte interface. In addition, the pH-dependent capacity (cd=f(pH)) turns out to be sensitiveto many micro- and macroscopic parameters, and for this reason one can detect some subtle interfacial transitionsby monitoring cd. In paper [H5] I showed how the methodology derived for and tested against the Monte Carlosimulations, can be applied to the previously published experimental data.

me

tal

oxi

de

2

(1- )z +

z

2

2

S HjO

S HjO

S HjO

S HjO

S HjO

S OHj

z

z

(1-z)+

(1- )z +

Ak

za,i

iC c,iz +

iC c,iz +

Ak

za,i

cds0 sd

ydy0

cd= capacity of EDL

Figure 6: Plane con-denser approximation ofthe e.d.l. ([H5])

The postulate of constant capacity is not the only approximation which rises some ques-tions. Unfortunately, there is a lack of empirical insight into the charged solid/aqueous phaseinterface on the atomistic level. For this reason, several (often too radical) approximation areused in a theoretical description of the e.d.l. formed at the metal oxide/electrolyte interface.For instance, on one hand we do not fully understand the charge formation process, but onthe other hand strikingly different in assumed protonation mechanism SCM models seemto equally well describe experimental data [27, 40, 41]. Similarly, the values of the partialcharge attributed to the surface sites in simple protonation models: 1-pK [16] and 2-pK [17]are lacking a deeper physical justification. Even though the more sound charge participationproposed in MUSIC and CD-MUSIC models [18, 42] take into account an actual surfaceoxygen atoms coordination and the chemical nature of the bonds they formed, the surfacerelaxation/reconstruction effects are still neglected. In my next paper [H6] I challenged thoseapproximations by using the ab-initio methods in combination with the Monte Carlo simu-lations for the rutile crystal (most stable form of TiO2). By using the wave-function/electrondensity population schemes and the ab-initio thermochemistry I was able to build a realistic microscopic model ofthe three most commonly exhibited crystal faces of rutile. Computational study confirmed that dissociative watersorption is a the most probable surface charging pathway, and the Monte Carlo simulation (based on ab-initioparametrization) provided an accurate prediction of the macroscopic (experimentally available) properties (i.e.,σ0=f(pH)).

So far, I have described the results obtained using the Grand Canonical Monte Carlo scheme. This methodis designed to model the static (time independent) equilibrium properties. In order to study protonation and ionsorption kinetics, I also started to use the Kinetic Monte Carlo algorithm (see [H7]). An interesting computationalfinding was the strong pH-dependence of relaxation time of proton sorption τθ, which was defined as ([H7] oraz[43]):

τθ =

∞∫

0

φθ(t)dt, where φθ(t) =〈θ(t; pH)〉 − 〈θ(∞; pH)〉

〈θ(0; pH)〉 − 〈θ(∞; pH)〉(2)

where φθ is a non-linear relaxation function, and θ(t; pH) represents the time-dependent extent of the surfaceprotonation. The kinetics of proton uptake shows clearly two time-scale regimes. After initial rapid uptakeof H+ ions, surface processes slow down, which is confirmed by the longer relaxation time. This kind of ratechanges in the metal oxide surface charging has been frequently observed experimentally, and it has been typicallyinterpreted as an evidence of the surface transformation processes (amorphization, dissolution, defect formation orrecrystallization) [3, 4, 44, 2, 45, 46]. In our next paper [H8] we were looking at the possible sources of such kineticdichotomy. We proved that the presence of two time-scale regimes is an inherent feature of the surface protonationand its appearance is not a manifestation of any second order phenomena. However, we also proved that thosesecond-order surface phenomena (surface transformation) make the two-time scale distinction more pronounced.

During my studies of electrical double layer formed at the metal oxide/electrolyte interface, the assumption ofthe Nernsitan surface response starts to become more and more questionable. It was widely accepted, that themetal oxide surface behaves similarly to the surface of ideal non-polarizable electrode (e.g., AgCl). This meansthat the change in the surface potential as a function of potential determining ion concentration (here H+ ions)may be quantitatively described using one of the following equations [47, 48]:

1

n(PZC − pH) =

eψ0

kBT+ arcsinh

(

eψ0

βkBT

)

(3)

where β is the parameter characteristic for a given interface, and n = 1/ ln(10). For the small values of eψ0/βkBT ,eq. (3) can be reduced to the linear version (an analogy of the Nernst equation, so called quasi-Nernst):

ψ0 = αkBT

ne(PZC − pH) , gdzie α =

β

1 + β(4)

Parameters β (eq. (3)) and α (eq. (4)) describe the deviation of the surface response from the ideal Nernstian one.That is, in the case of α equals 1, the system exhibits an ideal Nernstian response, and unit change in pH value is


accompanied by ∼ 59 mV drift in ψ0 (δψ0). The widespread usage of eqs. (3,4) was primarily dictated by the factthat they represent very simple functional relationship between surface potential and pH, whose application cantremendously reduce the mathematical complexity of the otherwise required solution of the Poisson-Boltzmannequation.

E1=E -ESCrE ref E2=E -E

aux ref

SC

rE e

lect

rod

e

refe

ren

ce e

lect

rod

e

au

xili

ary

ele

ctro

de

VV

single crystal

epoxy

resin

Hg

graphite

copper

wire

plexiglas

(a)

pH

0y

PZC

0

d 0y /dpH=const=59 mV

Nernstian response

d 0y /dpH=const<59 mV

quasi-Nernst

potential

d 0y /dpH=f(pH)

non-Nernstian response

(nonlinear potential)

d 0y /dpH<59 mV and d 0

y /dpH=const

(b)

3 4 5 6 7 8 9 10 11

pH

-0.05

0

0.05

0.1

0.15

0.2

y0[V

]

y0

10 mol/dm-3 3

10 mol/dm-1 3

experimental data from

Kallay, Preočanin 318 ( ) 290J. Colloid Interface Sci. 2008

dy0

a1=0.26, a × a × a ×

a × a ×

2 3 4

5 6

=-1.1 10 , =-2.2 10 , =1.3 10 ,

=-2.5 10 , =1.5 10

-2 -2 -2

-3 -4

a1=0.51, a × a × a ×

a × a ×

2 3 4

5 6

=-1.2 10 , =5 10 , =6.9 10 ,

=3.4 10 , =3.9 10

-1 -2 -3

-4 -6

(CIP)

(c)

Figure 7: Different types of electrode electro-static response (ψ0) to the pH changes (a), di-agram of the cell using single-crystal electrode(see Kallay and coworkers [49]) (b), fitting ofperturbation expression for ψ0 (c) (figures frompapers [H10,H11,H12])

Unfortunately, there has been more and more experimental facts sug-gesting the very different functional dependence ψ0=f(pH) than those of-fered by eqs. (3,4). In particular the measurements of surface potential ofsingle-crystal faces reported by Kallay and coworkers44 suggested thatthe profile ψ0=f(pH) is strongly non-linear [49].

Encouraged by prof. Kallay, I started to use molecular modelling tech-niques to determine the surface potential of the (001) hematite (α-Fe2O3)crystal face, with an attempt to compare my findings to the experimentalresults presented by Kallay’s group (see [H7]). By using the ab-initioparametrization (similar to [H6]) I showed that ψ0=f(pH) posses the non-linear features only at extreme pH values (i.e., at highly acidic or basicpH values). I also proved that the potential slope (parameter α in eq. (4))differs significantly from the ideal-Nernstian response, that is, it is closeto 0.5, whereas in most reported studies of polycrystalline systems, theα value was in the range (0.7; 1.0) (see [P28] and references therein).

Despite the fact, that I was unable to recreate the experimentalcurves; the computational findings provided a strong indication that theisolated crystal faces posses a completely different, and often very uniqueelectrochemical properties as compared with the polycrystalline elec-trode surfaces. As one can expect, those unique properties are crucialfor electrochemistry and electro-catalysis at the single crystal faces ofthe environmentally relevant minerals. Latter in my work I would comeback to the issue of surface potential at the (0010 hematite by usingmore advance experimental and mathematical methods (see [H12]).

Being intrigued by the specific electrostatic properties of the singlecrystal faces of mineral, we showed [H10] that there is a strong corre-lation between the macroscopic system descriptors (surface site density,ionic strength, energetic heterogeneity) and the non-Nernstian electroderesponse. Based on results of our simulation study, we derived a newperturbative expression for the surface potential as a function of pH, inan analogy to the Landau-Ginzubrg phase transition theory. We wereable to express free energy as a function of perturbative parameter ξthat describes the system deviation from an ideal reference state (ψ0=0,PZC). Finally, we expressed the surface potential as follows [H10]:

ψ0 =kBT

ne

(

α1ξ + α2ξ2 + α3ξ

3 + ...)

(5)

where

gdzie αi =1

i!

di∆G(ξ)

dξi, oraz ξ = n ln

[H+]

[H+]PZC(6)

This equation was then used to analyse the simulation results and ex-perimental data reported by Kallay and coworkers [49] (the same exper-imental data which I had previously tried to recreate using the latticeMonte Carlo modelling, see [H7]). The values of expansion coefficients

αi decrease with expansion order (i) in all considered cases. What is more, by comparing αi values we can quan-titatively compare the deviation from Nernstian response observed in various systems. The concepts discussedabove (papers [H7, H11, H10]) are illustrated in Figure 7.

44Department of Chemistry, University of Zagreb, Croatia


acidimetric

alkalimetric -+

PZC

3 4 5 6 7 8 9 10 11

pH

-200

-100

0

100

200

300

electrostaticsurfacepotential,ψ0/mV

(b) (c)Figure 8: Hysteresis loop in cyclic titration usingsingle-crystal electrode exposing the (001) hematite(α-Fe2O3) surface. Maxwell’s construction used toanalyse an electrochemical work done along the cycle(figures from papers [H11, H12]).

At the same time, I started the collaboration with an experi-mental teams measuring the electromotive force of the open-circuitwith a single-crystal electrode exposing only one crystal face to thesolution (Single-Crystal Electrode, SCrE) [50, 51, 49]. The experi-ments were carried out by Preocanin (Kallay’s group) and Chatman(Rosso’s group). The main difficulty in predicting surface potentialand the PZC value from the SCrE measurements is the fact thatthose quantities are not directly available. They have to be esti-mated a posteriori from the measured electromotive force of the cell(E) as a function of potential determining ions (e.g., for metal oxideE=f (pH)).

Measured E is converted to ψ0 by using an unknown factor ET

that represents all potential jumps in the system unrelated to theSCrE surface reactions (all Schottky and potential jumps related tothe resistivity of the other electrodes used in measurements, e.g.,auxiliary and/or reference electrode) [H11, H12]. We presented the current challenges in both theoretical andexperimental determination of the single-crystal face surface potential in a review article [H11] (at prof. Kallay’sinvitation).

Fe 1Odlugie

Fe 1Okrotkie

Fe 2O(a)

(b)

(c)

(d)

Figure 9: Surface sites exposedon the (001) hematite surface, andon the edges (a,b,c). AFM pictureof the electrode surface before thecyclic titration experiment. (fig-ures from paper [H12])

One of the solution we proposed to overcome the currently encountered short-comings, was based on the observation that the cyclic potentiometric titration of cellcomposed of the SCrE electrode often produces hysteresis loop (first time reportedin ref. [51]). We developed the method of analyzing titration loop, by taking anadvantage of the fact that the work done along the cyclic titration is proportionalto the hysteresis loop area (Fig. 8) [H11, H12]:

∆G ∝

∮

Ω(pH)

[

ψalk0 − ψacy

0

]

dpH ∝

∮

Ω(pH)

[

Ealk −Eacy]

dpH (7)

where Ealk, Eacy to measured electromotive force in alalimetric and acydimetrictitration loop, respectively (ψalk

0 , ψacy0 correspond to the converted values of sur-

face potential, ψ0 = E − ET ). By using the Maxwell construction of an equalareas we showed how the shifting constant ET can be correctly extracted from thecyclic measurements (illustrated for the (001) hematite, Fig. 8). In our work wedeliberately choose to work with the (001) hematite, because of its high stabil-ity, uniform termination by doubly coordinated surface oxygen atoms (Fe2O) andwidespread interest in geochemical community (along with the isomorphic (001) α-Al2O3) [52, 53, 54, 55, 56, 57, 58]. In our paper, we showed the thermodynamicderivation and justification for the proposed hysteresis loop decomposition schemeaccompanied by the simulation validation. We have also developed the computerprogram, which can be used to automatic hysteresis loop decomposition (see Sup-porting Information for the ref. [H12]). This software is currently used by bothexperimental teams (i.e., Rosso’s and Preocanin’s groups).

The analysis of the (001) hematite surface indicates that the PZC value is around8, and it is shifted toward the more acidic surface with respect to the theoretical prediction by two pH-units (MUSICmodel suggested PZC equals 6 [59]). The AFM analysis of the (001) α-Fe2O3 structure on the various stagesof titration procedure reveals that the kinks and traces are present on the surface. The surface sites exposed onthese defects are of a much lower acidity than those exposed on the flat (001) face (Fig. 9). The presence ofthese less-active sites results in the PZC value increase, but their estimated amount (fraction) is too low to fullyexplain the observed shift. The further measurements carried out by Chatman along with my theoretical analysis(paper [P1] in Section 2.1) proved that the electrostatic trapping of surface bound protons is an important factorin shifting the PZC value.

At the same time, by analysing the titration data reported by prof. Preocanin [60] I have developed an alternativemethod for the PZC determination suitable for non-hysteric cyclic-titration cases (see [H13]).

At present, I am still collaborating with dr. Chatman, prof. Rosso and prof. Preocanin (experimental teams)trying to improve our methods of the PZC value and surface potential determination from the SCrE measurements.


0 5 10 15 20 25 30 35 40 45 50 55

z / Å

-0.2

0

0.2

0.4

0.6

0.8

y(z

)/V

lAgCl

z z=0z

z=0

KCl + H O2

Ag

Cl

Figure 10: Electrostatic potential in the function of the dis-tance from the AgCl surface (averaged in the plane parallelto the surface) (papers [H14, H15]).

In early stages of the metal oxide/electrolyte interfacestudies, many theoretical concepts were developed based onthe experimental insight gained by using silver halides (AgX)[61, 6, 62, 63, 64]. It is widely accepted that the Ag|AgX andAgX (X=Cl,F,Br) electrodes are examples of the ideally non-polarizable ones, that is, they exhibit a rapid and stable elec-trochemical response to the change in potential determiningion (e.g., Ag+ or X−) concentration. It is believed that the sur-face potential of the AgX electrode behaves according to theNernst equation (α=1 in eq. (4)) [65]. However, the measure-ments using the single-crystal electrode showed that surfacepotential deviates from linearity for isolated crystal faces ofAgCl (for instance α∈(0.8;1.0), see [66, 67, 68]).

From the molecular point of view, the AgX/electrolyte interface is much easier to model than the metal ox-ide/electrolyte interface. The lack of protonable surface groups is highly beneficial because the non-dissociativewater models (e.g.. SPC/E [69, 70], TIP3P [71, 72] etc.) can be conveniently used to model the bulk aqueous phase.

3 4 5 6 7

z [angstrom]

-4

-3

-2

-1

0

1

2

3

4

Free

ener

gy[k

cal/m

ol]

4.28

3.2

4.95 5.4 5.85

a

b cd e

ec

b

a

a

b

c e

A

Figure 11: Free adsorption energy for K+ n ions atthe (001) AgCl surface being in contact with the KClelectrolyte solution (figure from paper [H14]).

The simplification arising from that fact, and the new intriguing ex-perimental results encourage us to use molecular dynamics to studythe electrostatics of the AgCl/electrolyte interface (see [H14, H15]).

In paper [H14], we showed both molecular dynamics simulationsand ab-initio (plane-wave) calculations of the AgCl/KCl electrolyteinterface. We developed new force-field model to correctly describethe crystal phase, elastic modules (Young, bulk), dielectric constantand in a reasonable way approximate the hydration free energy of theK+, Ag+ and Cl− ions. By comparing the classical45 and quantumapproaches, we showed that in many cases the quantum effects arenot necessary to describe the electrostatics of that interface. Oursimulations showed that there are two highly ordered water layersnear the AgCl surface (Fig. 10). The entropy of the water moleculesin those layers is much lower than in the bulk. This significantlylower mobility is due to the presence of a strong hydrogen bondnetwork (so called ice bilayer model [73, 74]). The ion adsorption

free energy profiles reveal that K+ ions prefer to form inner-sphere complexes, whereas Cl− ions are most likely tobe find in an outer-sphere complex geometry (Fig. 11). In this work, we showed how the electrostatic properties,ionic densities and water orientation are changing as a function of the distance from the surface (z; i.e., in directionnormal to the surface, Fig. 10). The charge density (σ(z)), electrostatic field (E(z)) and potential (ψ(z)) profilesare defined via the individual ionic density functions and the fixed partial charges (ρi(z), qi) as [75, 76, 77]:

σ(z) =∑

i

qiρi(z), E(z) =1

ǫ0

z∫

0

σ(ξ)dξ, ψ(z) = −1

ǫ0

∫

z∫

0

σ(ξ)dξ (8)

4 6 8 10 12 14 16 18 20 22

1

2

3

4

5

6

A

BcH

5 10 15 20 25

z [angstrom]

0

4

8

12

16

ca

pacity,

c(0

;z)

[mF

/cm

2]

capacity

Figure 12: Modelled electrostatic capac-ity of e.d.l. formed at the (001) AgCl/KClsolution, (B) comparison with Helmholtzmodel [H15]

We showed, that oscillations appearing in those profiles are a manifestation ofthe highly ordered water layers near the hydrophilic solid surface. The waterdipoles orient in such a way that electrostatic field and potential generatedby an excess electrolyte ions accumulated at the AgCl surface are effectivelyscreened. The rigid hydration layers near the AgCl surface, suggest that elec-trolyte ions near the surface are in a relatively different environment than thosein the bulk phase (regarding polarity, i.e., bulk dielectric constant). In addition,the presence of such a rigid charge distribution confirms the applicability of theHelmholtz model to describe the AgCl/electrolyte interface. In our next paper[H15], we confirmed that the value of dielectric constant near the (001) AgClsurface is indeed much lower (ǫpow=5.1) than in the bulk phase, which can beinterpreted as an evidence of the dielectric saturation near the AgCl surface.

45statistical mechanics modelling using an analytical model of interactions; force-field


reactants

ET transition

structure

products

reaction

coordinate, x

en

erg

y

ET

structureFe

+2 +3/Fe Fe

+3 +2/Fe

2VAB

DG*'

l

DG*

x=0 x=1x=0.5

x

Figure 13: Marcus’ model of electrontransfer [78, 79, 80, 81, 82] (rysunek zpracy [H16])

In addition, we showed that the simulated capacity (cint=8.43 µF/cm2) isquite close to the experimentally determined one for a similar surface (i.e.,for AgI [62]). Although the modelled capacity profile (cd=f(z), Fig. 12) canbe fitted by the Helmholtz model, there are some subtle fluctuations (oscil-lations), which again clearly indicate the ordering water structure near theAgCl surface.

So far in my study, I have not considered the electron transfer processesat the mineral surface. In other words, I was assuming that surface charge isformed due to the surface groups protonation and electrolyte ions accumula-tion, but there is no red-ox transitions affecting this charge distribution.

However, the charge transfer process at the metal oxide surface arecrucial for many environmentally relevant phenomena (corrosion, enzymaticreactions, photo-degradation, precipitation/dissolution) [83, 84, 85]. Be-cause the metal oxide/electrolyte interface is highly non-uniform, there isa well documented difficulty in determining the key factors governing elec-tron transfer between adsorbed ion and the surface atom. For this rea-son, we have started our modelling by using a simple prototypical sys-tem, that is, a minimalistic representation of hematite (α-Fe2O3) in aform of the hydrated dimer Fe2O11 (paper [H16]). In this work we ap-plied the Marcus theory of electron transfer [78, 79, 80, 81, 82], in whichthe solvent reorganization due to the flow of charge density from elec-tron donor to acceptor is decomposed into the inner46 and outer47 reorganization energy [82] (Fig. 13).Marcus model assumes the presence of two well localized quantum states representing the donor/acceptorpair before48 and after49 charge transfer, as well as the intermediate50 degenerated quantum state [83, 82].

-12 -9 -6 -3 0 3 6 9 12

N-áNñ

-10

-8

-6

-4

-2

logP

(N)

r

r=3 Å, N 21.7, N (14;28)á ñ= Î

r=4 Å, N 36.4, N (30;43)á ñ= Î

r=5 Å, N 60.1, N (50;69)á ñ= Î

r=6 Å, N 96.1, N (85;108)á ñ= Î

Figure 14: Gaussian fluctuations of water den-sity around prototypical α-Fe2O3 dimeric sys-tem [H16]

The hight of energy barrier along the electron transfer path dependson the solvent reorganization energy (λ) and electronic coupling (VAB)between the reactants and products wave-functions at the crossing point(i.e., transition state geometry). With respect to the coupling magnitude(VAB), one can distinguish two limiting cases of adiabatic charge transfer(strong coupling) and non-adiabatic51 (week coupling). In paper [H16] weshowed, that in the case of our prototypical system the electron transfercan be described using the adiabatic regime, however, the poor quality ofthe basis set used to represent the wave-function may led to the oppo-site conclusion. In the adiabatic approximation, the electron transfer rateconstant (kET ) is given by the following expression: [82, 83, 84, 85]

kET = νn exp

[

−1

kBT

(

(

λ+∆G0)2

4λ− VAB

)]

(9)

where ∆G0 is the free energy change and νn is the frequency of molecular vibration along the charge transferpathway. In paper [H16] we showed how different computational approaches drastically differ in an estimatedvalue of the rate constant (kET ). In particular, we showed that an error related to the cheap (poor) wave-functionrepresentation may be larger than kBT .52 We proved, that Marcus’ approach to reorganization energy may beeffectively improved by including the Born-Kirkwood-Onsanger multi-pole expansion coefficients. In addition,our calculations suggest that the Self-Consistent Reaction Field model (implicit solvent) proposed by Klamt(Conductor-like Screening Model) [86] can give as accurate estimation of the reorganization energy as the explicitmolecular dynamics using the Umbrella Sampling methodology (in our work we implemented the computationalscheme proposed by Warshel et al. [87, 88, 89]).

46geometrical changes within the first solvation sphere47geometrical changes in the external solvation spheres48reactants49products50or transition51or diabatic52kBT at T=273K is equal to 0.593 kcal/mol (2.479 kJ/mol)


An important aspect of the study [H16] is a validation of the linear solvent response assumption (requiredcondition for the applicability of the Marcus’ model). We investigated the solvent linear response by analysing theenergy gap auto-correlation function and the solvent fluctuation statistics in the first and other hydration spheresaround prototypical dimer (Fig. 14).

In our work [H16], we showed how the isotopic effects may influence the electron transfer kinetics, using themethodology proposed in our previous work (paper [P15] in Section 2.1). We proved, that entropic contribution tothe overall energetics of charge transfer is relatively small, and the enthalpic change is a driving force for electronhopping from the donor to acceptor [H16].

2.4.3 Accomplishments of research selected to support the habilitation application

• we proved that surface complexation models developed for the metal oxide surfaces can to correctly describeexperimental data obtained for the clay materials that posses the permanent bulk charge due to the isomorphicsubstitutions (paper [H1])

• I showed, how local energetic and topological correlations affects charge density curves, and how the long-range electrostatic interactions can effectively screened those local correlations (papers [H2, H3, H5])

• I presented a new statistical, mean-field description of the energetic non-uniformity and electrostatics withinthe framework of the integral adsorption isotherm ([H4])

• I showed, how ab-initio methods can be used to parametrize the microscopic simulation model of the metaloxide/electrolyte interface ([H6, H9])

• I proved that kinetic dichotomy (two time-scale regimes) in surface protonation is an inherent interfaceproperty, and the secondary surface transformations make that kinetic division more pronounced (papers[H7, H8])

• by using simulations, I showed the non-linearity of the surface potential for the single-crystal faces and Iproposed a new perturbative expression for the surface potential (paper [H9, H10])

• I developed a new mathematical method of analyzing cyclic potentiometric titration which allows to determinethe surface potential and PZC for the hysteric systems with a single-crystal electrode. I also developed analternative method for the electrochemical systems with the rapid surface electrochemical response that doesnot exhibit hysteresis in a cyclic titration (papers [H11, H12, H13])

• I proved that first hydration layers are strongly oriented near the hydrophilic AgCl surface, and forms thebilayer ice-type structure. I showed that the presence of such strong orientation of water molecules manifestsitself in the electrostatic properties of the AgCl/KCl electrolyte solution interface (papers [H14, H15])

• I provide energetic evidence that K+ ion prefer to form an inner-sphere complex, and the Cl− ion is morelikely to form an outer-sphere complex at the AgCl/electrolyte interface (paper [H14])

• I showed how molecular dynamics may be used to determine the electrostatic capacity of the AgCl/electrolyteinterface, and I demonstrated that simulation predictions are very close to the experimental results obtainedfor a similar system (paper [H15])

• By using simulations I proved that water in the first hydration layer near the AgCl surface is in dielectricsaturation state, which was also confirmed by the low dielectric constant at the interface (paper [H15])

• I presented the comprehensive, critical analysis of computational methods for calculating electron transferin a prototypical dimeric system as a model of ferric iron oxide. I identified the possible error sources. Ihave also showed that isotopic fractionation has a pronounce charge-transfer signature, and I confirmed thatenthalpy is a driving force of charge transfer (paper [H16])


2.4.4 Summary and conclusions

By looking at papers selected to support habilitation application (Section 2.1, 2.2), one can notice a cleartendency towards more rigorous molecular representation of the mineral/electrolyte solution interface. At thebeginning of my scientific work, I used mainly analytical models and lattice Monte Carlo simulations. Latter, Iadded the ab-initio calculations in order to get a physically meaningful model parametrization. In my simulationstudies, I went from the generalized lattice model of the sorbent surface and continuous dielectric approximationof the bulk electrolyte phase to the explicit (i.e., all atoms) representation. Along with expanding the theoreticaltools used in my study, I have also changed the type, scale and importance of the solved problems. This wasdirectly related to a closer collaboration with experimental groups, which for instance, resulted in developing anew mathematical method of analysing electrochemical experimental data. In addition, I also started to use thesimulation/theoretical methods to provide the numerical hints and suggestions for the further laboratory tests. Theconsolidation of experimental and simulation study is the main theme of my ongoing research projects (see papers[P2, P3, P4] from list in Section 2.1 and the description of current projects in Section 3.2).

2.4.5 Future research directions

My future research plans are strictly related to my current projects.53 In a longer run, my research is focusedon molecular modelling of enzymatic processes, in particular those occurring at the mineral surface.54 I am alsointerested in the charge transfer at the metal oxide/electrolyte interface, including the reductive ferric iron oxidedissolution.

References

[1] G. E. Brown, V. E. Henrich, W. H. Casey, D. L. Clark, C. Eggleston, A. Felmy, D. W. Goodman, M. Gratzel,G. Maciel, M. I. McCarthy, K. H. Nealson, D. A. Sverjensky, M. F. Toney, and J. M. Zachara. Metal oxidesurfaces and their interactions with aqueous solutions and microbial organisms. Chem. Rev., 99(1):77–174,1999.

[2] D. L. Sparks. Environmental Soil Chemistry. Academic Press, Amsterdam, 2 edition, 2002.

[3] D. A. Dzombak and F. M. M. Morel. Surface Complexation Modeling: Hydrous Ferric Oxide. Wiley, Hoboken,1 edition, 1990.

[4] J. Lutzenkirchen, editor. Surface Complexation Modelling, volume 11. Academic Press, Amsterdam, 2006.

[5] A. K. Karamalidis and D. A. Dzombak. Surface Complexation Modeling: Gibbsite. Wiley, Hoboken, 1 edition,2010.

[6] J. Lyklema. Fundamentals of Interface and Colloid Science: Solid-Liquid Interfaces, volume II. AcademicPress, London, 1 edition, 1995.

[7] Principles of Colloid and Surface Chemistry. P. C. Hiemenz and R. Rajagopalan. CRC Press, New York, 3edition, 1997.

[8] M. J. Rosen and J. T. Kunjappu. Surfactants and Interfacial Phenomena. Wiley, Hoboken, 4 edition, 2012.

[9] G. Sposito. On points of zero charge. Environ. Sci. Technol., 32(19):2815–2819, 1998.

[10] G. Sposito. The Chemistry of Soils. Oxford University Press, Oxford, 2 edition, 2008.

[11] G. Sposito. The Surface Chemistry of Natural Particles. Oxford University Press, Oxford, 2004.

[12] R. M. Cornell and U. Schwertmann. The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses.Wiley, Weinheim, 2 edition, 2003.

[13] G. A. Parks and P. L. de Bruyn. The zero point of charge of oxides. J. Phys. Chem., 66(6):967–973, 1962.

53see Section 3.2 and my grants in Section 1.154see our papers [P2, P4] in Section 2.1, as well as the on-going projects in Section 3.2.4


[14] M. Kosmulski. volume 102 of Surfactant Science Series. CRC Press, Boca Raton, 2001.

[15] M. Kosmulski. Surface Charging and Points of Zero Charge, volume 145 of Surfactant Science Series. CRCPress, Boca Raton, 2009.

[16] W.H. van Riemsdijk, J.C.M. de Wit, L.K. Koopal, and G.H. Bolt. Metal ion adsorption on heterogeneoussurfaces: Adsorption models. J. Colloid Interface Sci., 116(2):511–522, 1987.

[17] J. A. Davis and J. O. Leckie. Surface ionization and complexation at the oxide/water interface ii. surfaceproperties of amorphous iron oxyhydroxide and adsorption of metal ions. J. Colloid Interface Sci., 67(1):90–107, 1978.

[18] T. Hiemstra, W.H Van Riemsdijk, and G.H Bolt. Multisite proton adsorption modeling at the solid/solutioninterface of (hydr)oxides: A new approach: I. model description and evaluation of intrinsic reaction constants.J. Colloid Interface Sci., 133(1):91–104, 1989.

[19] M. Borkovec. Origin of 1-pk and 2-pk models for ionizable water-solid interfaces. Langmuir, 13(10):2608–2613,1997.

[20] M. Cernık, M. Borkovec, and J. C. Westall. Affinity distribution description of competitive ion binding toheterogeneous materials. Langmuir, 12(25):6127–6137, 1996.

[21] M. Kobayashi, F. Juillerat, P. Galletto, P. Bowen, and M. Borkovec. Aggregation and charging of colloidalsilica particles: Effect of particle size. Langmuir, 21(13):5761–5769, 2005.

[22] C. Labbez, B. Jonsson, M. Skarba, and M. Borkovec. Ion-ion correlation and charge reversal at titrating solidinterfaces. Langmuir, 25(13):7209–7213, 2009.

[23] G. Koper and M. Borkovec. Binding of metal ions to polyelectrolytes and their oligomeric counterparts: Anapplication of a generalized potts model. J. Phys. Chem. B, 105(28):6666–6674, 2001.

[24] W. Rudzinski, R. Charmas, S. Partyka, F. Thomas, and J.Y. Bottero. On the nature of the energetic surfaceheterogeneity in ion adsorption at a water oxide interface: the behavior of potentiometric, electrokinetic, andradiometric data. Langmuir, 8(4):1154–1164, 1992.

[25] W. Rudzinski, R. Charmas, S. Partyka, and J. Y. Bottero. On the nature of the energetic surface heterogeneityin ion adsorption at a water/oxide interface: theoretical studies of some special features of ion adsorption atlow ion concentrations. Langmuir, 9(10):2641–2651, 1993.

[26] R. Charmas. Four-layer complexation model for ion adsorption at energetically heterogeneous metal ox-ide/electrolyte interfaces. Langmuir, 15(17):5635–5648, 1999.

[27] W. Piasecki, W. Rudziński, and R. Charmas. 1-pk and 2-pk protonation models in the theoretical descriptionof simple ion adsorption at the oxide/electrolyte interface: A comparative study of the behavior of the surfacecharge, the individual isotherms of ions, and the accompanying electrokinetic effects. J. Phys. Chem. B,105(40):9755–9771, 2001.

[28] R. Sips. On the structure of a catalyst surface. J. Chem. Phys., 16:490–495, 1948.

[29] R. Sips. On the structure of a catalyst surface. 2. J. Chem. Phys., 18:1024–1026, 1950.

[30] M. Jaroniec and R. Madey. Physical Adsorption on Heterogeneous Solids. Elsevier, Amsterdam, 1988.

[31] W. Rudziński and D. H. Everett. Adsorption of Gases Heterogeneous Surfaces. Academic Press, London, 1991.

[32] W. Rudziński, W. A. Steele, and G. Zgrablich, editors. Equilibria and Dynamics of Gas Adsorption on Het-erogeneous Solid Surfaces. Studies in Surface Science and Catalysis. Elsevier, Amsterdam, 1996.

[33] J. Reszko-Zygmunt, S. Sokołowski, D. Henderson, and D. Boda. Temperature dependence of the double layercapacitance for the restricted primitive model of an electrolyte solution from a density functional approach. J.Chem. Phys., 122:084504–1/23, 2005.


[34] D. di Caprio, Z. Borkowska, and J. Stafiej. Simple extension of the gouy–chapman theory including hard sphereeffects.: Diffuse layer contribution to the differential capacity curves for the electrode/electrolyte interface. J.Electroanal. Chem., 2003:17–23, 540.

[35] S. Lamperski. Semi-empirical modelling of the properties of the electrode/electrolyte interface in the presenceof specific anion adsorption. Electrochim. Acta, 41(14):2089–2095, 1996.

[36] K. R. Painter, P. Ballone, M. P. Tosi, P. J. Grout, and N. H. March. Capacitance of metal-molten-salt interfaces.Surf. Sci., 133(1):89–100, 1983.

[37] D. Hendersona. Simulation and theory of the electrochemical double layer for strong ionic interactions. J.Mol. Liq., 92(1-2):29–39, 2001.

[38] D. Boda, D. Henderson, K-Y. Chan, and D. T. Wasan. Low temperature anomalies in the properties of theelectrochemical interface. Chem. Phys. Lett., 308(5-6):473–478, 1999.

[39] M. Holovko, V. Kapko, D. Henderson, and D. Boda. On the influence of ionic association on the capacitanceof an electrical double layer. Chem. Phys. Lett., 341(3-4):363–368, 2001.

[40] W. Piasecki. Determination of the parameters for the 1-pk triple-layer model of ion adsorption onto oxidesfrom known parameter values for the 2-pk tlm. J. Colloid Interface Sci., 302(2):389–395, 2006.

[41] J. Lutzenkirchen. Comparison of 1-pk and 2-pk versions of surface complexation theory by the goodness of fitin describing surface charge data of (hydr)oxides. Environ. Sci. Technol., 32(20):3149–3154, 1998.

[42] T. Hiemstra and W.H. Van Riemsdijk. A surface structural approach to ion adsorption: The charge distribution(cd) model. J. Colloid Interface Sci., 179(2):488–508, 1996.

[43] M. E. J. Newman and G. T. Barkema. Monte Carlo Methods in Statistical Physics. Oxford University Press,New York, 1999.

[44] D. E. Yates. The structure of the oxide/aqueous electrolyte interface. PhD thesis, University of Melbourne,1975.

[45] Y. G. Berube, G. Y. Onoda, and P. L. De Bruyn. Proton adsorption at the ferric oxide/aqueous solution interface:Ii. analysis of kinetic data. Surf. Sci., 7(3):448–461, 1967.

[46] M. Duc, F. Adekola, G. Lefevre, and M. Fedoroff. Influence of kinetics on the determination of the surfacereactivity of oxide suspensions by acid–base titration. J. Colloid Interface Sci., 303(1):49–55, 2006.

[47] L. Bousse, N. F. de Rooij, and P. Bergveld. Operation of chemically sensitive field-effect sensors as a functionof the insulator-electrolyte interface. IEEE Trans. Electron Devices, 30(10):1263–1270, 1983.

[48] R. E. G. van Hal, J. C. T. Eijkel, and P. Bergveld. A general model to describe the electrostatic potential atelectrolyte oxide interfaces. Adv. Colloid Interface Sci., 69(1-3):31–62, 1996.

[49] N. Kallay and T. Preocanin. Measurement of the surface potential of individual crystal planes of hematite. J.Colloid Interface Sci., 318(2):290–295, 2008.

[50] N. Kallay, Z. Dojnovic, and A. Cop. Surface potential at the hematite-water interface. J. Colloid Interface Sci.,286(2):610–614, 2005.

[51] T. Preocanin, A. Cop, and N. Kallay. Surface potential of hematite in aqueous electrolyte solution: Hysteresisand equilibration at the interface. J. Colloid Interface Sci., 299(2):772–776, 2006.

[52] C. M. Eggleston and G. Jordan. A new approach to ph of point of zero charge measurement: crystal-facespecificity by scanning force microscopy (sfm). Geochim. Cosmochim. Acta, 62(11):1919–1923, 1998.

[53] T. Hiemstra and W. H. Van Riemsdijk. Effect of different crystal faces on experimental interaction force andaggregation of hematite. Langmuir, 15(23):8045–8051, 1999.


[54] A. G. Stack, S. R. Higgins, and C. M. Eggleston. Point of zero charge of a corundum-water interface probedwith optical second harmonic generation (shg) and atomic force microscopy (afm): New approaches to oxidesurface charge. Geochim. Cosmochim. Acta, 65(18):3055–3063, 2001.

[55] J. P. Fitts, X. Shang, G. W. Flynn, T. F. Heinz, and K. B. Eisenthal. Electrostatic surface charge ataqueous/α-al2o3 single-crystal interfaces as probed by optical second-harmonic generation. J. Phys. Chem.B, 109(16):7981–7986, 2005.

[56] L. Zhang, C. Tian, G. A. Waychunas, and Y. R. Shen. Structures and charging of α-alumina (0001)/waterinterfaces studied by sum-frequency vibrational spectroscopy. J. Am. Chem. Soc., 130(24):7686–7694, 2008.

[57] B. Braunschweig, S. Eissner, and W. Daum. Molecular structure of a mineral/water interface: Effects ofsurface nanoroughness of α-al2o3 (0001). J. Phys. Chem. C, 112(6):1751–1754, 2008.

[58] J. Lutzenkirchen, R. Zimmermann, T. Preocanin, A. Filby, T. Kupcik, D. Kuttner, A. Abdelmonem, D. Schild,T. Rabung, M. Plaschke, F. Brandenstein, C. Werner, and H. Geckeis. An attempt to explain bimodal behaviourof the sapphire c-plane electrolyte interface. Adv. Colloid Interface Sci., 157(1-2):61–74, 2010.

[59] P. Venema, T. Hiemstra, P. G. Weidler, and W. H. Van Riemsdijk. Intrinsic proton affinity of reactive surfacegroups of metal (hydr)oxides: Application to iron (hydr)oxides. J. Colloid Interface Sci., 198(2):282–295, 1998.

[60] J. Lutzenkirchen, T. Preocanin, F. Stipic, F. Heberling, J. Rosenqvist, and N. Kallay. Surface potential at thehematite (001) crystal plane in aqueous environment and the effect of prolonged aging in water. submitted toGeochim. Cosmochim. Acta, 2013.

[61] J. O’M. Bockris, A. K. N. Reddy, and M. E. Gamboa-Aldeco. Modern Electrochemistry 2A: Fundamentals ofElectrodics, volume 2A. Springer, New York, 2 edition, 2001.

[62] J. Lyklema and J. Th. G. Overbeek. Electrochemistry of silver iodide the capacity of the double layer at thesilver iodide-water interface. J. Colloid Sci., 16(6):595–608, 1961.

[63] J. Lyklema. Geometrical factors in the capacity of the electrical double layer. Kolloid Z. Z. Polym., 175(2):129–134, 1961.

[64] J. Lyklema. Electrical double layer on silver iodide. influence of temperature and application to sol stability.Discuss. Faraday Soc., 42:81–90, 1966.

[65] I. Larson and P. Attard. Surface charge of silver iodide and several metal oxides. are all surfaces nernstian?J. Colloid Interface Sci., 227(1):152–163, 2000.

[66] N. Kallay, T. Preocanin, and F. Supljika. Measurement of surface potential at silver chloride aqueous interfacewith single-crystal agcl electrode. J. Colloid Interface Sci., 327(2):384–387, 2008.

[67] T. Preocanin, F. Supljika, and N. Kallay. Evaluation of interfacial equilibrium constants from surface potentialdata: Silver chloride aqueous interface. J. Colloid Interface Sci., 337(2):501–507, 2009.

[68] T. Preocanin, F. Supljika, and N. Kallay. Charging of silver bromide aqueous interface: Evaluation of interfacialequilibrium constants from surface potential data. J. Colloid Interface Sci., 346(1):222–225, 2010.

[69] P. G. Kusalik and I. M. Svishchev. The spatial structure in liquid water. Science, 265(5176):1219–1221, 1994.

[70] H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma. The missing term in effective pair potentials. J. Phys.Chem., 91(24):6269–6271, 1987.

[71] M. W. Mahoney and W. Jorgensen. A five-site model for liquid water and the reproduction of the densityanomaly by rigid, nonpolarizable potential functions. J. Chem. Phys., 112(20):8910–8922, 2000.

[72] W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein. Comparison of simple potentialfunctions for simulating liquid water. J. Chem. Phys., 79(2):926–935, 1983.

[73] D. L. Doering and T. E. Madey. The adsorption of water on clean and oxygen-dosed ru(011). Surf. Sci.,123(2-3):305–337, 1982.


[74] T. E. Madey and J. T. Yates. Evidence for the conformation of h2o adsorbed on ru(001). Chem. Phys. Lett.,51(1):77–83, 1977.

[75] E. Spohr. Molecular simulation of the electrochemical double layer. Electrochim. Acta, 44(11):1697–1705,1999.

[76] E. Spohr. Molecular dynamics simulations of water and ion dynamics in the electrochemical double layer.Solid State Ionics, 150(1-2):1–12, 2002.

[77] E. Spohr. Some recent trends in computer simulations of aqueous double layers. Electrochim. Acta, 49(1):23–27, 2003.

[78] R. A. Marcus. Theory of electron transfer reaction rates of solvated electrons. J. Phys. Chem., 43(10):3477–3489, 1965.

[79] R. A. Marcus. On the theory of oxidation reduction reactions involving electron transfer. i. J. Phys. Chem.,24(5):966–978, 1956.

[80] R. A. Marcus. On the theory of oxidation reduction reactions involving electron transfer. ii. applications todata on the rates of isotopic exchange reactions. J. Phys. Chem., 26(4):867–871, 1957.

[81] R. A. Marcus. On the theory of oxidation reduction reactions involving electron transfer. iii. applications todata on the rates of organic redox reactions. J. Phys. Chem., 26(4):872–877, 1957.

[82] R. A. Marcus. Electront ransfer reactions in chemistry. theory and experiment. Rev. Mod. Phys., 65(3):599–610,1993.

[83] V. Balzani, P. Piotrowiak, M. A. J. Rodgers, J. Mattay, D. Astruc, H. B. Gray, J. Winkler, S. Fukuzumi, T. E.Mallouk, Y. Haas, A. P. de Silva, and I. Gould, editors. Electron Transfer in Chemistry, Principles, Theories,Methods, and Techniques, volume 1-5. Wiley-VCH, Weinheim, 2001.

[84] R. J. D. Miller, G. L. McLendon, A. J. Nozik, W. Schmickler, and F. Willig. Surface Electron Transfer Processes.Wiley-VCH, New York, 1995.

[85] A. M. Kuznetsov and J. Ulstrup. Electron Transfer in Chemistry and Biology: An Introduction to the Theory.Wiley, Chichester, 1999.

[86] A. Klamt. Conductor-like screening model for real solvents: A new approach to the quantitative calculationof solvation phenomena. J. Phys. Chem., 99(7):2224–2235, 1995.

[87] A. Warshel. Dynamics of reactions in polar solvents. semiclassical trajectory studies of electron-transfer andproton-transfer reactions. J. Chem. Phys., 86(12):2218–2224, 1982.

[88] J. K. Hwang and A. Warshel. Microscopic examination of free-energy relationships for electron transfer inpolar solvents. J. Am. Chem. Soc., 109(3):715–720, 1987.

[89] G. King and A. Warshel. Investigation of the free energy functions for electron transfer reactions. J. Chem.Phys., 93(12):8682–8692, 1990.


3 Teaching, collaboration and science outreach activity

3.1 Teaching

My teaching experience is limited to my PhD studies (period of time between 2002 and 2005). Since 2005till now, I have not had any teaching obligations.

3.2 International collaboration

In the past, I was collaborating with the following scientists: prof. James Rustad,55 prof. William Casey,56 prof.David Chandler,57 Kris Szornel,58 dr. Sebastien Kerisit,59 prof. Nikola Kallay,60 prof. Frederic Villieras,61 prof.Fabien Thomas63 oraz prof. Benedicte Prelot.62

Currently, I am involved in a realization of five projects in an international collaboration, which are brieflydescribed bellow.

3.2.1 Project: Metal oxide nanoparticles coated by organic ligands

In this project we are looking at the electron injection from the excited surface-boundfluorescence day molecules to the surface atoms of metal oxide nanoparticle. Trappingof this excess charge in the form of the small polaron and its thermally-limited diffusion(hopping between cation sites inside nanoparticle). In particular, we are interested in theacid-base properties of metal oxide nanoparticle in the presence of electron donors, shift indye pKa values due to the binding to the metal oxide surface, and size-dependent stability ofnanoparticles. It is continuation of our previous ab-initio studies of small polaron formationin semiconducting ferric oxides (see paper [P3] in Section 2.1). This project is bases onthe collaboration with: prof. Gilbert (Lawrence Berkeley National Laboratory, CA, USA),prof. Rosso (Pacific Northwest National Laboratory, WA, USA), prof. Preocanin (Universityof Croatia, Zagreb), prof. Lewiński (IChF PAS Warsaw) oraz prof. Piasecki (AWF Warsaw).

3.2.2 Project: Non-equilibrium electrochemistry at the single-crystal electrode/electrolyteinterface

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In collaboration with prof. Rosso and dr. Chatman (Pacific Northwest NationalLaboratory, WA, USA) I am looking at the non-equilibrium processes occurring atthe single-crystal electrode surface exposed to a small perturbation caused by thespontaneous charge flow in a closed electrochemical cell. It is a continuation of ouron-going collaboration (see papers [P1, P7, P8] in Section 2.1), and it is inspiredby the research initiated by Yanina and Rosso.63 They showed that if two single-crystal electrodes selectively exposing different crystal faces are connected (closedcircuit), the charge starts to flow with simultaneous dissolution of one surface andprecipitation process occurring on the other.63 This current decays exponentiallywith time and our preliminary studies suggest that surface dissolution/precipitationis probably accompanied by the electrochemical splitting of water (production of

H2 and O2). My role in this project is to provide the theoretical model and interpretation of the experimentallycollected data in prof. Rosso’s laboratory.

55Department of Geology, University of California, Davis, CA, US56Department of Chemistry, University of California, Davis, CA, US57Department of Chemistry, University of California, Berkeley, CA, US58Lawrence Berkeley National Laboratory, Berkeley, US59Pacific Northwest National Laboratory, Richland, US60Department of Chemistry, University of Zagreb, Croatia61Laboratoire Environnement et Mineralurgie, CNRS/INPL, Vandoeuvre-les-Nancy Cedex, France62Institut Charles Gerhard Montpellier CNRS, Universite Montpellier II, Montpellier, France63S. Yanina, K. Rosso Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction Science 320(5878):218-222,

2008.


3.2.3 Project: Protein pore (α-hemolysin) conductivity perturbations

A

This project is supported by the Foundation for Polish Science (Mentoring program,edition 2012), and is conducted in a collaboration with prof. Bayley’s group (OxfordUniversity, UK). In this project I am going to use the molecular dynamics to study theblocking events of the protein channel formed by the α-hemolysin, and related to thatchanges in electronic conductance across channel. One of the intriguing aspect, is theorientation and binding of the cyclodextrine molecule inside the protein channel. Thecyclodextrine molecule trapped inside the protein pore is a sensitive sensor for thesmaller molecules passing through the channel, this fact can be used in designing aneffective nanomolecular chemical detector device.

3.2.4 Project: Double electrical layer and charge transfer processes in bological systemse-

a)

b)

In this project we are looking at the electronic conductance, charge trans-fer and membrane protein docking of the outer-membrane decaheme cytochrome iso-lated from Shewanella Oneidensis MR-1. It is a continuation of my on-goingcollaboration with prof. Rosso (Pacific Northwest National Laboratory, WA, USA)(see papers [P2,P4] in Section 2.1). In contrast to our previous studies, herewe are trying to implement a much more realistic representation of the outer-membrane (lipopolysaccharide layer) of the Gram-negative bacteria (S. Oneiden-sis).

3.2.5 Project: Non-innocent ligands in enzymatic charge transfer

11 Å

In this project I collaborate with prof. Solomon’s group (Stanford University, CA, USA),on the research projects related to the NCN grant project (see current grants in Section 1.1).By using molecular dynamics and ab-initio methods, we are trying to determine the freeenergy of electron and proton transfer between uncoupled cooper sites in peptidylglycineα-hydroxylating monooxygenase (aPHM).


3.3 Science outreach acvity

3.3.1 Conference organizing

In 2011, I co-organized with prof. Rosso (PNNL) the microsymposium devoted to the biological aspects ofelectron transfer at the mineral surfaces (Electron Transfer at Mineral Surfaces and Biogeochemical Implications)during the 242nd ACS National Meeting & Exposition (Denver, Colorado US, 28th of August - 1st of September,2011). This session was organized within the Division of Geochemistry (GEOC) American Chemical Society, andit was composed of 16 oral presentations, including my own lecture.64

3.3.2 Participation in domestic conferences

2013 Piotr Zarzycki Interfacial/bulk charge transfer in environmentally relevant systems.Mikrosympozjum sprawozdawcze Instytutu Chemii Fizycznej PANJanuary 8-10, 2013, Warsaw

2012 Piotr Zarzycki Molecular Dynamics of solvent effect on reduction potential of biologicallyrelevant systems. Sesja sprawozdawcza-szkoleniowa użytkowników KDM-ICMApril 19-21, 2012, Sterdyń

3.3.3 Participation in international conferences

2012 P. Zarzycki Effect of membrane proteins on water ordering near the biological membranesX GIRONA SEMINAR on Theoretical and Computational Chemistry for the Modelling of BiochemicalSystems: From Theory to Applications, July 2-9, 2012, Girona, Spain

2011 P. Zarzycki, M. Breuer, J. Blumberger, D. Richardson, T. Clarke, M. Edwards, K. Rosso,Molecular modeling of electronic conductance through a microbial c-type decaheme cytochrome.242nd ACS National Meeting & Exposition, 28th of August to 1st of September, 2011Denver, Colorado, USA; lecture was a part of micro-symposium co-organized with prof. Rosso entitled:Electron Transfer at Mineral Surfaces and Biogeochemical Implications.

2011 K. Rosso, P. Zarzycki, M. Breuer, J. Blumberger, L. Shi, D. Richardson, T. Clarke,M. Edwards, J. Butt, J. Zachara, J. FredricksonLarge-Scale Simulation of Molecular Structure and Electron Transfer in Microbial CytochromesGoldschmidt 2011 Conference, Prague, Czech Republic, September 14-19, 2011The lecture abstract was published in the form of publication:65

• K. Rosso, P. Zarzycki, M. Breuer, J. Blumberger, L. Shi, D. Richardson, T. Clarke, M. Edwards,J. Butt, J. Zachara, J. FredricksonLarge-Scale Simulation of Molecular Structure and Electron Transfer in Microbial CytochromesMineralogical Magazine 75(3) (2011) 1757 (Impact Factor of this journal equals 1.3)

2011 K. Rosso, P. Zarzycki, C. Pearce, J. Katz, B. Gilbert, R. Handler, M. Scherer, P. MeakinReactive Fe(II) and Electron Exchange Dynamics in Iron OxidesGoldschmidt 2011 Conference, Prague, Czech Republic, September 14-19, 2011An abstract was published in:65

• K. Rosso, P. Zarzycki, C. Pearce, J. Katz, B. Gilbert, R. Handler, M. Scherer, P. MeakinReactive Fe(II) and Electron Exchange Dynamics in Iron OxidesMineralogical Magazine 75(3) (2011) 1757 (Impact Factor of this journal equals 1.3)

2011 M. Breuer, P. Zarzycki, K. M. Rosso, J. BlumbergerThermodynamics of electron flow in the bacterial decaheme cytochrome MtrF

3rd Quantum BioInorganic Chemistry Conference, Cesky Krumlov, Czech Republic, June 25-28, 2011

64see Participation in international conferences, Section 3.3.365this publication is NOT included in the publication lists presented in Sections 2.1, 2.2.


2010 S. Chatman, P. Zarzycki, T. Preocanin, K. RossoElectrostatic potentials and charge distributions at structurally defined Hematite/electrolyte interfaces.Goldschmidt 2010 Conference, Knoxville, Tennessee (USA), 13-18 czerwca 2010An abstract was published in:65

• S. Chatman, P. Zarzycki, T. Preocanin, K. RossoElectrostatic potentials and charge distributions at structurally defined Hematite/electrolyte interfaces.Geochimica et Cosmochimica Acta 74(11) (2010) Supplement 163(Impact Factor of this journal is equal to 4.259)

2010 P. Zarzycki, S. ChatmanPoint of Zero Potential of Individual Crystal Faces of Hematite fromSingle-Crystal Electrode MeasurementSecond Annual PostDoc Poster Session Pacific Northwest National Laboratory, Richland WA (USA),July 13-15, 2010

2009 P. Zarzycki, S. Kerisit, F. N. Skomurski, K. M. RossoTheoretical description of electron exchange dynamics at Fe(II)/goethite interfaces237th ACS National Meeting, Salt Lake City, UT (USA), March 22-26, 2009in session Molecular Computational Geochemistry for Water-Rock Interactions

2009 P. ZarzyckiMolecular Dynamics study of electrical double layer formation at the silver chloride/electrolyte interfaceFirst Annual PostDoc Poster Session Pacific Northwest National Laboratory, Richland WA (USA),September 25-27, 2009

2009 P. Zarzycki, S. Kerisit, K. RossoTheoretical study of ferrous-ferric electron transfer reactions in aqueous solutionsand at the iron oxide-water interface.12th International Conference on the Chemistry and Migration Behaviour of Actinides and FissionProducts in the Geosphere (MIGRATION’09), Kennewick, Washington (USA), September 20-25, 2009

2007 P. ZarzyckiQuantum statistics of liquid waterThe 2007 Berkeley Mini Statistical Mechanics Meeting,University of California, Berkeley, (CA, USA), January 12-14, 2007symposium was dedicated to the 65th birthday of m prof. Andersen (Stanford University)


Acknowledgements

I would like to express my gratitude to my closest family (wife Anita and son Kacper) for their love and support.

I am grateful to prof. Robert Charmas, prof. Paweł Szabelski and prof. Wojtek Piasecki for their help in startingoff my scientific carrier, their kindness and friendship.

I thank Kevin Rosso (PNNL), David Chandler (UC Berkeley), James Rustad (US Davis), Edward Solomon(Stanford), Hagan Bayley (Oxford) and prof. Janusz Lewiński (IPC PAS) for giving me an opportunity to learn anddevelop by working in their research groups.

I would also like to thank the Head of the Institute of Physical Chemistry (IPC PAS, Warsaw) prof. RobertHołyst and the Leader of the IPC-PAS Research Team ”Coordinate complexes and functional materials” prof.Janusz Lewiński for giving me opportunity to continue my research in IPC (IPC PAS Warsaw).


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