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**and Fluctuation Theorems**

Hyunggyu Park 박 형 규 朴 炯 奎 Entropy production and Fluctuation Theorems Nonequilibrium processes Brief History of Fluctuation theorems Jarzynski equality & Crooks FT Experiments Trajectory-dependent entropy & FTs Ending Tutorial Lecture at PTES2013, Tongji U, Shanghai, China (August 29, 2013) [Bustamante]

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**Nonequilibrium processes**

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., … Thermodynamic 2nd law - law of entropy increase or irreversibility 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. 1st law Themodyn. 2nd law**

System Themodyn. 2nd law Phenomenological law Total entropy does not change during reversible processes. Total entropy increases during irreversible (NEQ) processes. Jarzynski equality ▶ Work and Free energy

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**Jarzynski equality & Fluctuation theorems**

Simplest derivation in Hamiltonian dynamics state space 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

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**Jarzynski equality & Fluctuation theorems**

Crooks ``detailed”fluctuation theorem odd variable time-reversal symmetry for deterministic dynamics Crooks detailed FT for PDF of Work ``Integral”FT

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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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PNAS 106, (2009)

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**Trajectory-dependent entropy production**

state space trajectory time-rev

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**Total entropy production and its components**

System

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**Fluctuation theorems Integral fluctuation theorems**

System Integral fluctuation theorems Thermodynamic 2nd laws Detailed fluctuation theorems

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**Probability theory Consider two normalized PDF’s :**

state space trajectory Consider two normalized PDF’s : Define “relative entropy” Integral fluctuation theorem (exact for any finite-time trajectory)

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**Probability theory Consider the mapping : Require**

reverse path Consider the mapping : Require Detailed fluctuation theorem (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 reverse path NEQ steady state (NESS) for fixed

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**If odd-parity variables are introduced ???**

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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), ..

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