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Hyunggyu Park
Introduction to Fluctuation Theorems 1. Nonequilibrium processes
2. Brief History of Fluctuation theorems
3. Jarzynski equality & Crooks FT
4. Experiments
5. Probability theory viewpoint on FTs
6. Ending Colloquium at PSI at Pyeong Chang (July 10, 2013)
[Bustamante]
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Nonequilibrium processes
Thermodynamic 2nd law
- law of entropy increase or irreversibility
Why NEQ processes?
- biological cell (molecular motors, protein reactions, …)
- electron, heat transfer, .. in nano systems
- evolution of bio. species, ecology, socio/economic sys., ...
- moving toward equilibrium & NEQ steady states (NESS)
- interface coarsening, ageing, percolation, driven sys., …
NEQ Fluctuation theorems
- go beyond thermodynamic 2nd law & many 2nd laws.
- some quantitative predictions on NEQ quantities (work/heat/EP)
- experimental tests for small systems
- trivial to derive and wide applicability for general NEQ processes
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Brief history of FT (I)
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Brief history of FT (II)
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Thermodynamics
Themodyn. 2nd law
Themodyn. 1st law
System
Phenomenological law
▶ Work and Free energy
Total entropy does not change during reversible processes.
Total entropy increases during irreversible (NEQ) processes.
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Jarzynski equality & Fluctuation theorems
Themodyn. 2nd law
Can we have any more information on W for general non-equilibrium processes?
2
1
V
P
Distribution of W, P(W) for a given protocol? Any “equality” relation, regarding to W ?
Jarzynski equality
s R
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Jarzynski equality & Fluctuation theorems
Simplest derivation in Hamiltonian dynamics
-Intial distribution must be of Boltzmann (EQ) type. -Hamiltonian parameter changes in time. (special NE type). -In case of thermal contact (stochastic) ?
crucial
generalized still valid
state space
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Jarzynski equality & Fluctuation theorems
Crooks ``detailed”fluctuation theorem
time-reversal symmetry for deterministic dynamics
Crooks detailed FT for PDF of Work
``Integral”FT
odd variable
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Experiments
DNA hairpin mechanically unfolded by optical tweezers
Collin/Ritort/Jarzynski/Smith/Tinoco/Bustamante, Nature, 437, 8 (2005)
Detailed fluctuation theorem
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arXiv:1105.0416 Electron transport - full counting
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PNAS 106, 10116 (2009)
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March meeting, 2012
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arXiv: 1008.1184
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Total entropy production and its splittings
System
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Probability theory viewpoint
on Fluctuation theorems
Seifert, PRL 95, 040602 (2005)
Esposito/VdBroeck, PRL 104, 090601 (2010)
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Fluctuation theorems ??
Integral fluctuation theorems
System
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Fluctuation theorems
Integral fluctuation theorems
Detailed fluctuation theorems
Thermodynamic 2nd laws
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Probability theory
• Consider two normalized PDF’s : state space
trajectory
• Define “relative entropy”
Integral fluctuation theorem
(exact for any finite-time trajectory)
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Probability theory
• Consider the mapping :
• Require
Detailed fluctuation theorem
reverse path
(exact for any finite t)
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Dynamic processes
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Stochastic dynamics s R
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Reservoir entropy change Schnakenberg/Hinrichsen
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Fluctuation theorems
NEQ steady state (NESS)
for fixed
reverse path
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Ending
Remarkable equality in non-equilibrium (NEQ) dynamic processes, including Entropy production, NEQ work and EQ free energy.
Turns out quite robust, ranging over non-conservative deterministic system, stochastic Langevin system, Brownian motion, discrete Markov processes, and so on.
Still source of NEQ are so diverse such as global driving force, non-adiabatic volume change, multiple heat reservoirs, multiplicative noises, nonlinear drag force (odd variables), and so on.
Validity and applicability of these equalities and their possible modification (generalized FT) for general NEQ processes.
More fluctuation theorems for classical and also quantum systems
Still need to calculate P(W), P(Q), … for a given NEQ process.
Effective measurements of free energy diff., driving force (torque), ..
Gravity is an entropic force ??? [Verlinde)