Nonequilibrium Thermodynamics of Small Systems: Classical and Quantum Aspects. Massimiliano Esposito
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1 Nonequilibrium Thermodynamics of Small Systems: Classical and Quantum Aspects Massimiliano Esposito Paris May 9-11, 2017
2 Introduction Thermodynamics in the 19th century: Thermodynamics in the 21th century: 2
3 Challenges when dealing with small systems Small systems Large fluctuations Quantum effects (low temperatures) Far from equilibrium (large surf/vol ratio) Average behavior contains limited information Higher moments or full probability distribution is needed Linear response theories fail Nonlinear response and nonperturbative methods need to be developed Stochastic thermodynamics Traditional stochastic descriptions fail Stochastic descriptions taking coherent effects into account are needed 3
4 Outline Part I: Stochastic Thermodynamics: From fluctuation theorems to stochastic efficiencies Part II: Thermodynamics of Information Processing Part III: Quantum Thermodynamics 4
5 Part I: Stochastic Thermodynamics: From fluctuation theorems to stochastic efficiencies 1) Stochastic thermodynamics 2) Universal fluctuation relation 3) Finite-time thermodynamics 4) Efficiency fluctuations 5
6 1) Stochastic thermodynamics Esposito and Van den Broeck, Phys. Rev. E 82, (2010) Esposito, Phys. Rev. E 85, (2012) Driving Markovian master equation: Energy and Matter currents reservoir. reservoir Different reservoirs Local detailed balance: 6
7 Energy Particle number Shannon entropy 1st law: Energy balance Mechanical work Driving Particle balance Chemical work System 2nd law: Entropy balance Heat flow Entropy production Entropy change in the reservoirs reservoir. reservoir Slow driving with 1 reservoir: equilibrium thermo iff (detailed balance) 7
8 2) Universal Fluctuation Relation Energy balance: Particle balance: Entropy balance: Time-reversed driving Time-reversed trajectory Integral fluctuation theorem: not a physical observable 8
9 Involution Detailed FT for entropy production if Seifert, PRL (2005) Fluctuation theorem for physical observable? res w sys res sys Driving + 1 reservoir + start at equilibrium: Work FT (Crooks FT) res No driving + multiple reservoirs + longtime limit res Driving + multiple reservoirs + start at equilibrium vs reservoir : Current FT w res sys res Work FT Bulnes Cuetara, Esposito, Imparato, PRE 89, (2014) : Current FT 9
10 Isothermal example: driven junction Bulnes Cuetara, Esposito, Imparato, PRE 89, (2014) Setup: res w sys Initial condition: equilibrium vs a reference reservoir res Mechanical work: res Chemical work: w sys Crooks FT res (valid for any time) sys res Current FT 10
11 Fluctuation Relation: Synthesis Fluctuations in small out-of-equilibrium systems satisfy a universal symmetry Everything can also be done for: - Fokker-Planck dynamics - Open quantum systems (weak coupling) FT can be used: to derive Onsager reciprocity relations and generalizations to derive fluctuation-dissipation relations and generalizations to check the consistency of a transport theory to calculate free energy differences Nonequilibrium fluctuations, fluctuation theorems and counting statistics in quantum systems, Esposito, Harbola, Mukamel, Rev. Mod. Phys. 81, 1665 (2009) Ensemble and Trajectory Thermodynamics: A Brief Introduction, Van den Broeck and Esposito, Physica A 418, 6 (2015) 11
12 3) Finite-time thermodynamics a) Steady state energy conversion Thermoelectricity: Reservoir entropy change: sys hot cold Entropy production (entropy change in the reservoirs): Efficiency: Thermoelectric effect if: Power: General formulation: intput ouput 12
13 b) Energy conversion in the linear regime Linear regime: Maximum efficiency: Maximum is reached at tight coupling: vanishing power! Efficiency at maximum power: 13
14 c) Efficiency at maximum power beyond linear regime Phenomenological models I. I. Novikov & P. Chambadal (1957). F. Curzon and B. Ahlborn, Am. J. Phys. 43, 22 (1975). Linear (In case of tight coupling) Van den Broeck, Phys. Rev. Lett. 95, , (2005) Nonlinear (In presence of a left-right symmetry) Esposito, Lindenberg, Van den Broeck, Phys. Rev. Lett. 102, (2009) 14
15 Exactly solvable models using stochastic thermodynamics Thermoelectric quantum dot Esposito, Lindenberg, Van den Broeck, EPL 85, (2009) cold Photoelectric nanocell Rutten, Esposito, Cleuren, Phys. Rev. B 80, (2009) hot 15
16 Finite-Time Thermodynamics: Synthesis Stochastic thermodynamics naturally combines kinetics and thermodynamics Powerful formalism to study energy transduction at the nanoscale It allows to: - Unambiguously define thermodynamic efficiencies (connected to EP) - Distinguish the system specific features from the universal ones - View very different devices (bio., chem., meso.) from the same global perspective
17 4) Efficiency fluctuations Verley, Esposito, Willaert, Van den Broeck, The unlikely Carnot efficiency, Nature Communications 5, 4721 (2014) phonons sun photons filled sun lead r lead l phonons Ensemble averaged description: filled empty At the trajectory level: Fluctuation theorem: What can we say about? 17
18 a) Long time efficiency fluctuations Carnot is the least probable efficiency!!! FT: Macroscopic efficiency is the most probable efficiency 18 Verley, Esposito, Willaert, Van den Broeck, The unlikely Carnot efficiency, Nature Communications 5, 4721 (2014)
19 Verley, Esposito, Willaert, Van den Broeck, The unlikely Carnot efficiency, Nature Communications 5, 4721 (2014) The least likely efficiency is the Carnot efficiency: Consequence of FT! Carnot efficiency 19
20 b) Finite-time efficiency fluctuations Polettini, Verley, Esposito, Finite-time efficiency fluctuations: Enhancing the most likely value, PRL 114, (2015) At : Lorentzian with max After critical time, the distribution becomes bimodal: - local min goes to - local max goes to infinity : - global max goes to and The distribution has no moments: Tight coupling: no efficiency fluctuations 20
21 c) Long-time efficiency fluctuations in quantum systems Esposito, Ochoa, Galperin, Efficiency fluctuation in quantum thermoelectric devices, PRB 91, (2015) Cumulant GF (heat & work) Fluctuation relation t=s s=0 s=-0.8t 21
22 Efficiency fluctuations: Synthesis Finite-time thermodynamics at the fluctuating level Accurate characterization of energy transduction at the nanoscale Experimental verification: Martinez, Roldan, Dinis, Petrov, Parrondo, Rica, Brownian Carnot engine, Nature Physics DOI: /NPHYS3518 (2015) Proesmans, Dreher, Gavrilov, Bechhoefer, Van den Broeck, Brownian duet: A novel tale of thermodynamic efficiency, Phys. Rev. X 6, (2016) The long time results can be generalized: - to time-asymmetric drivings Verley, Willaert, Van den Broeck, Esposito, Universal theory of efficiency fluctuations, PRE 90, (2014) Gingrich, Rotskoff, Vaikuntanathan, and Geissler, Efficiency and Large Deviations in Time-Asymmetric Stochastic Heat Engines, NJP 16, (2014) - to quantum systems (NEGF approach) Esposito, Ochoa, Galperin, Efficiency fluctuation in quantum thermoelectric devices, PRB 91, (2015) Agarwalla, Jiang, Segal, Full counting statistics of vibrationally-assisted electronic conduction: transport and fluctuations of the thermoelectric efficiency, PRB 92, (2015) The finite-time behavior: Polettini, Verley, Esposito, Finite-time efficiency fluctuations: Enhancing the most likely value, PRL 114, (2015) Proesman, Cleuren, Van den Broeck, Stochastic efficiency for effusion as a thermal engine, EPL 109, (2015) 22 Jiang, Agarwalla, Segal, Efficiency Statistics and Bounds for Systems with Broken Time-Reversal Symmetry, PRL 115, (2015)
23 Part II: Thermodynamics of Information Processing 1) Stochastic thermodynamics - Nonequilibrium thermodynamics - Landauer principle - Nonequilibrium state as a resource 2) Measurement and feedback - Szilard engine - Erasure with feedback 3) Bipartite perspective - Nonautonomous (measurement and feedback) - Autonomous (information flow) 4) Conclusions and perspectives 23
24 1) Stochastic Thermodynamics Open system dynamics work heat System E,S Reservoir T Master equation: may depend on time Local detailed balance: 0th law Equilibrium: 24
25 Nonequilibrium Thermodynamics Energy: Entropy: 1st law Energy change Work Heat 2nd law Entropy production Entropy change Entropy change in the reservoir 25
26 Landauer principle Heat expelled: Work needed: 26
27 Optimal erasure in finite time Accuracy-dissipation trade-offs: Power: Efficiency: 27 Finite-time erasing of information stored in fermionic bits, Diana, Bagci, Esposito, Phys. Rev. E 85, (2012)
28 Nonequilibrium state as a resource Nonequilibrium free energy 1st law + 2nd law : if eq. to eq. Pure waist: 0 x 0 Optimal extraction: x Second law and Landauer principle far from equilibrium, Esposito and Van den Broeck, EPL 95, (2011)
29 2) Measurement and feedback Phenomenological approach Measurement Mutual Information Feedback without feedback 29
30 Ex1: Szilard engine Energy plays no role: Measurement Feedback 30
31 Ex2: Erasure with feedback in finite time 31 Finite-time erasing of information stored in fermionic bits, Diana, Bagci, Esposito, Phys. Rev. E 85, (2012)
32 3) Bipartite perspective Non-autonomous systems (measurement and feedback) Mutual Information Perfect measurement Measurement Feedback Resetting memory 32 Sagawa, Ueda PRL 102, (2009)
33 Autonomous systems (continuous information flow) Steady state: Thermodynamics with continuous information flow, Horowitz and Esposito, Phys. Rev. X 4, (2014) At steady state see also Hartich, Barato, Seifert, JSM P02016 (2014) 33
34 Ex: Two coupled quantum dots where Maxwell demon limit: Thermodynamics of a physical model implementing a Maxwell demon, Strasberg, Schaller, Brandes, Esposito, Phys. Rev. Lett. 110, (2013) 34
35 35 Thermodynamics with continuous information flow, Horowitz and Esposito, Phys. Rev. X 4, (2014)
36 4) Conclusions and perspectives Thermodynamics of information, Parrondo, Horowitz, Sagawa, Nature Physics 11, 131 (2015) Many other approaches Esposito and Schaller, EPL 99, (2012) Mandal, Jarzynski, PNAS 109, (2012) Barato, Seifert, PRL (2014) Horowitz, Sandberg, NJP 16, (2012) Experiments Toyabe & al., Nature Physics 6, 988 (2010) Bérut & al., Nature 483, 187 (2012) Jun, Gavrilov, Bechhoefer, PRL 113, (2014) Koski & al. PRL 115, (2015) Biology (sensing, proofreading, chemotaxis, chemical computing... ) 36
37 Part III: Quantum Thermodynamics 1) Phenomenological thermodynamics 2) A Hamiltonian formulation 3) Born-Markov-Secular Quantum Master Equation (QME) 4) Landau-Zener QME 5) Repeated interactions 6) More... 37
38 1) Phenomenological Nonequilibrium Thermodynamics system Zeroth law: System dynamics with an equilibrium 1st law: Slow transformation 2nd law: Entropy production (dissipation) 38
39 2) Hamiltonian formulation System X System Y 39
40 System X Reservoir R Assumption: 1st law: 2nd law: [Esposito, Lindenberg, & Van den Broeck, NJP 12, (2010)] 40
41 Ideal reservoir Another identity: Summary: 1st, 2nd law, strong coupling no 0th law, but not 41
42 3) Born-Markov-Secular QME slow weak Effective dynamics Local detailed balance: 42
43 Thermodynamics Energy: Entropy: 1st law 2nd law Summary: 0th, 1st, 2nd law, but weak coupling, slow trsf. 43
44 4) A Landau-Zener approach Prob. diabatic transition: Validity: [Barra & Esposito, PRE 93, (2016)] 44
45 Effective dynamics Master equation Local detailed balance p(t) Exact vs stochastic dynamics t [Barra & Esposito, PRE 93, (2016)] 45
46 Thermodynamics 1st law 2nd law [Barra & Esposito, PRE 93, (2016)] 46
47 between crossing at crossing QM adiabatic regime (slow driving) At the crossing: From : Reversibility only occurs if: [Barra & Esposito, PRE 93, (2016)] 47
48 QM diabatic regime (fast driving) [Barra & Esposito, PRE 93, (2016)] 48
49 [Barra & Esposito, PRE 93, (2016)] 49
50 Work fluctuations Jarzynski and Crooks fluctuation relation System initially at equilibrium P(w m ) Full system: two point measurement approach vs System: stochastic trajectory approach m w 10 [Barra & Esposito, PRE 93, (2016)] 50
51 QM diabatic regime: continuous limit Pauli master equation with Fermi golden rule rates [Barra & Esposito, PRE 93, (2016)] 51
52 5) Repeated interactions Exact identities [Strasberg, Schaller, Brandes & Esposito, PRX 7, (2017)] 52
53 T S Un+1 Un Un 1 1st law 2nd law [Strasberg, Schaller, Brandes & Esposito, PRX 7, (2017)] 53
54 Repeated interaction QME T S Un+1 Un Un 1 Effective dynamics Effect of a kick: [Strasberg, Schaller, Brandes & Esposito, PRX 7, (2017)] 54
55 Thermodynamics 1st law 2nd law thermodynamics cannot always be deduced from dynamics alone [Strasberg, Schaller, Brandes & Esposito, PRX 7, (2017)] 55
56 Units entropy changes Approach 1: Approach 2: Different by Thermal units Fraction of units which interacted mixing contribution ideal reservoir [Strasberg, Schaller, Brandes & Esposito, PRX 7, (2017)] 56
57 More... Quantum master equation including degenerate states: [Bulnes-Cuetara, Esposito & Schaller, Entropy 18, 447 (2016)] Fast periodic driving using master equation and Floquet theory: [Bulnes-Cuetara, Engel & Esposito, NJP 18, 447 (2016)] Strong coupling using polaron transformation and quantum master equation: [Krause, Brandes, Esposito & Schaller, JCP 142, (2015)] [Schaller, Krause, Brandes & Esposito, NJP 15, (2013)] Strong coupling using Nonequilibrium Green s functions: [Esposito, Ochoa & Galperin, PRL 114, (2015)] [Esposito, Ochoa & Galperin, PRB 92, (2015)] Strong coupling (classical) using time scale separation: [Strasberg & Esposito, arxiv: ] [Esposito, Phys. Rev. E 85, (2012)] 57
58 Perspectives Stochastic thermodynamics in the thermodynamic limit Interplays between N and t Chemical Reaction Networks (Stochastic & Deterministic) Toward energy and information processing in biology Thank you 58
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