ADVANCES IN

QUANTUM CHEMISTRYRECENT ADVANCES IN COMPUTATIONAL CHEMISTRY

EDITOR-IN-CHIEF

PER-OLOV LÖWDIN

PROFESSOR EMERITU S

DEPARTMENT OF QUANTUM CHEMISTRY

AND

QUANTUM THEORY PROJECT

UPPSALA UNIVERSITY

UNIVERSITY OF FLORID AUPPSALA, SWEDEN

GAINESVILLE, FLORID A

EDITOR S

JOHN R. SABIN AND MICHAEL C . ZERNER

QUANTUM THEORY PROJECT

UNIVERSITY OF FLORID A

GAINESVILLE, FLORIDA

GUEST EDITORS

JACEK KARWOWSKI

MATI KARELSO N

DEPARTMENT OF PHYSICS

DEPARTMENT OF CHEMISTRYNICHOLAS COPERNICUS UNIVERSITY

UNIVERSITY OF TARTUTORUN, POLAND

TARTU, ESTONIA

VOLUME 28

Contributors

xiiPreface

x vConference Participants

xviiIntroductory Remarks

xix

Diatomic Molecules : Exact Solutions of HF EquationsJacek Kobu s

1. Introduction

22. FD HF Method Development

33. The Calibration of Basis Sets

44. Full CI with Numerical Orbitals

65. One-Electron Diatomic States

76. Future Developments

97. Summary

1 08. Acknowledgments

1 1References

1 1

Perturbation Theory for Low-Spin Open-Shell State sXiangzhu Li and Josef Paldu s

1. Introduction

1 62. Basic Formalism

1 73. Mpller-Plesset UGA Based PT

1 94. Epstein-Nesbet UGA Based PT

2 25. Applications

2 46. Conclusions

3 07. Acknowledgments

3 0References

3 0

The Contracted Schrödinger Equation : Some ResultsC. Valdemoro, L . M. Tel, and E . Perez-Romero

1. Introduction

342. Theoretical Outline

3 53. RDM's Approximations

3 84. Computational Details

42

5. Results and General Discussion

4 36. Acknowledgments

4 5References

45

Distributed Gaussian Basis Sets : Some Recent Results and Prospect s

S. Wilson and D. Moncrieff

1. Introduction

4 82. Basis Sets for Atoms

493. Distributed Gaussian Basis Sets

5 04. Independent Particle Models

5 15. Electron Correlation Effects

5 56. Summary and Prospects

5 87. Acknowledgments

5 9References

5 9

The Nuclear Motion Problem in Molecular Physic s

B . T. Sutcliffe

1. Introduction

6 62. The Schrödinger Equation for Bound Molecular States

6 83. Separating Electronic and Nuclear Motions

7 4

4. The Relationship of Nuclear Motion to Electronic Structure

7 65. Conclusions

7 9References

7 9

Combining Quantum Chemistry and Molecular Simulatio n

Florian Milller-Plath e

1. Introduction

8 22. Hybrid Method

8 33. The Conformations of Dimethoxy Ethane in Aqueous Solution

844. Prospects and Loose Ends

8 6References

8 7

Solvent Effects from a Sequential Monte Carlo-QuantumMechanical Approac h

Kaline Coutinho and Sylvio Canut o

1 . Introduction

90

2. Monte Carlo Simulation

923. Sequential Monte Carlo-Quantum Mechanical Analysis

954. Summary

1025. Acknowledgments

103References

103

Energy Deposition of Swift Alphas in Neon : An Electron NuclearDynamics StudyJohn R . Sabin

1. Introduction

1082. Theory

11 03. Results

11 44. Summary

11 75. Acknowledgments

11 7References

11 7

Theoretical Modeling of Spectra and Collisional Processes of Weakl yInteracting ComplexesRobert Moszynski, Tino G. A. Heijmen, Paul E . S . Wormer, andAd van der Avoird

1. Introduction

1202. Ab Initio Potential Energy Surfaces

12 13. Ab Initio Interaction-Induced Properties

12 34. Applications

1255. Summary and Conclusions

13 8References

13 8

Quantum Chemical Treatment of Molecules in CondensedDisordered MediaMati Karelson

1. Introduction

1422. Aqueous Free Energies of Solvation of Organic Compounds

1453. Tautomeric Equilibrium Constants

1504. Dipole Moments and Charge Distribution

15 25. Conclusions

15 4References

154

Determining the Shapes of Molecular Electronic Bands from Thei rIntensity Distribution Moments

Dorota Bielinska-WWz and Jacek Karwowsk i

1. bltroduction

16 02. General Theory

16 23. One-Dimensional Problems

16 34. Results

16 55. Summary

16 86. Acknowledgments

16 8References

16 8

Convergence of Symmetry-Adapted Perturbation Theory for theInteraction between Helium Atoms and between a HydrogenMolecule and a Helium Atom

Tatiana Korona, Robert Moszynzki, Bogumil Jeziorski

1. Introduction

17 22. Method

17 33. Computational Details

17 74. Numerical Results and Discussion

17 8References

18 6

Electron Affinity of SF6

M. Klobukowski, G . H. F. Diercksen, and J . M. Garcia de la Vega

1. Introduction

19 02. Calculations Using Standard Basis Sets

19 23. Development of Extended Basis Sets

19 44. Calculations with Optimized Basis Sets

19 75. Summary

19 96. Acknowledgments

200References

200

The Oxonium Rydberg Radical : Electronic Transitions

C. Lavin and I . Martin

1. Introduction

2062. Computational Procedure

2083. Results and Analysis

21 14. Concluding Remarks

216

5 . Acknowledgments

216References

217

An ab initio Study of Four-Membered Rings. Boranes HBXYBH ;(X, Y = C, N, O )Borislava Batandjieva, Ingrid Miadokovä, and Ivan Cernusäk

1. Introduction

2202. Computational Details

22 13. Results and Discussion

2244. Summary

23 25. Acknowledgments

23 2References

23 2

SiN 2 and SiN 4 Molecules : An ab Intio Study of Molecular an dElectronic Structure, Stability, and IR ActivityRudolf Janoschek

1 . Introduction

2362 . Computational Methods

2373 . Computational Results

23 84. Conclusions

243References

244

A Sternheimer-like Response Property of the Bromine Molecule :Electric Field Dependence of the Br Field Gradien tP. W. Fowler, S . A . Peebles, and A . C . Legon

1. Introduction

24 82. Ab Initio Calculations on Br2

2483. Ab Initio Calculations on H3 N• • .Br2

25 14. The Townes-Dailey Model

25 15. An Empirical Value for the Response Tensor gzz Z (Br)

25 3References

255

Molecular Properties of Boron-Coinage Metal Dimers : BCu,BAg, BAuMaria Barysz and Miroslav Urban

1 . Introduction

258

2. Basis Sets and Computational Methods

25 9

3. Results and Discussion

26 2

4. Conclusions

26 9

5. Acknowledgments

270

References

270

Decades of Theoretical Work on Protonated Hydrate s

E. Kochanski, R . Kelterbaum, S . Klein, M. M. Rohmer, and A . Rahmouni

1. Introduction

274

2. Historical Evolution of Theoretical Studies on PH

274

3. Theoretical Treatments and Techniques

27 5

4. The Results

28 0

5. Conclusion

28 6References

286

Density Functional Theory : A Useful Tool for the Study of FreeRadicals

Oscar N. Ventura, Martina Kieninger, and Kenneth Irvin g

1. Introduction

294

2. Geometrical Structure of Simple Radicals

297

3. Thermodynamics

299

4. Reactivity

30 1

5. Conclusions

30 6

6. Acknowledgments

30 6

References

30 6

Guesses-Hunches-Formulae-Discoveries

B . G. Wybourne

1. Introduction

31 2

2. Spinors and the Rotation Group

31 2

3. Reduced Notation and the Symmetric Group

31 3

4. Kronecker Products for Two-Row Shapes

314

5. n-Noninteracting Particles in a Harmonic Oscillator Potential

31 5

6. Concluding Remarks

31 7

7. Acknowledgments

31 7

References

317

Applying Artificial Intelligence in Physical Chemistr yF. J . Smith, M. Sullivan, J . Collis, and S . Loughlin

1. Introduction

3202. Nature of Knowledge

32 13. Related Work

32 34. Object Oriented Knowledge Representation

3235. Manipulation of Data

32 56. Example of AI Technique

3257. Application to Molecular Computations

326References

32 7

Artificial Intelligence Support for Computational Chemistry

Wkodzislaw Duc h

1. Introduction

3302. What Can AI Offer?

33 23. Feature Space Mapping

33 64. Classification of Computational Chemistry Results

33 95. Summary

34 2References

342

Abstract Data Types in the Construction of Knowledge-Base dQuantum Chemistry SoftwareP. L . Kilpatrick and N . S . Scott

1. Introduction

34 62. Abstract Data Types and Production Rules

34 63. An ADT and Its Associated Production Rule Set for a Simple

Configuration Interaction Expansion Problem

35 04. Summary

35 85. Acknowledgments

35 9References

35 9

Index

361