Chemical Physics Theory Group, Department of Chemistry and Center for Quantum Information and Quantum Control,University of Toronto, Toronto, Canada M5S 3H6(Dated: January 8, 2014)Contrary to the conventional wisdom that deviations from standard thermodynamics originatefrom the strong coupling to the bath, it is shown that these deviations are intimately linked to thepower spectrum of the thermal bath. Speci cally, it is shown that the lower bound of the dispersionof the total energy of the system, imposed by the uncertainty principle, is dominated by the bathpower spectrum and therefore, quantum mechanics inhibits the system thermal-equilibrium-statefrom being described by the canonical Boltzmann’s distribution. This is in sharp contrast to theclassical case, for which the thermal equilibrium distribution of a system interacting via centralforces with pairwise-self-interacting environment, irrespective of the interaction strength, is shown tobe exactly characterized by the canonical Boltzmann distribution. As a consequence of this analysis,we de ne an e ective coupling to the environment that depends on all energy scales in the systemand reservoir interaction. Sample computations in regimes predicted by this e ective coupling aredemonstrated. For example, for the case of strong e ective coupling, deviations from standardthermodynamics are present and, for the case of weak e ective coupling, quantum features such asstationary entanglement are possible at high temperatures.
Chemical Physics Theory Group, Department of Chemistry and Center for Quantum Information and Quantum Control,University of Toronto, Toronto, Canada M5S 3H6(Dated: January 8, 2014)Contrary to the conventional wisdom that deviations from standard thermodynamics originatefrom the strong coupling to the bath, it is shown that these deviations are intimately linked to thepower spectrum of the thermal bath. Speci cally, it is shown that the lower bound of the dispersionof the total energy of the system, imposed by the uncertainty principle, is dominated by the bathpower spectrum and therefore, quantum mechanics inhibits the system thermal-equilibrium-statefrom being described by the canonical Boltzmann’s distribution. This is in sharp contrast to theclassical case, for which the thermal equilibrium distribution of a system interacting via centralforces with pairwise-self-interacting environment, irrespective of the interaction strength, is shown tobe exactly characterized by the canonical Boltzmann distribution. As a consequence of this analysis,we de ne an e ective coupling to the environment that depends on all energy scales in the systemand reservoir interaction. Sample computations in regimes predicted by this e ective coupling aredemonstrated. For example, for the case of strong e ective coupling, deviations from standardthermodynamics are present and, for the case of weak e ective coupling, quantum features such asstationary entanglement are possible at high temperatures.
Contrary to the conventional wisdom that deviations from standard thermodynamics originate from the strong coupling to the bath, it is shown that in quantum mechanics, these deviations originate from the uncertainty principle and are supported by the non-Markovian character of the dynamics. Specifically, it is shown that the lower bound of the dispersion of the total energy of the system, imposed by the uncertainty principle, is dominated by the bath power spectrum; therefore, quantum mechanics inhibits the system thermal-equilibrium-state from being described by the canonical Boltzmann's distribution. We show for a wide class of systems, systems interacting via central forces with pairwise-self-interacting environments; this general observation is in sharp contrast to the classical case, for which the thermal equilibrium distribution, irrespective of the interaction strength, is exactly characterized by the canonical Boltzmann distribution; therefore, no dependence on the bath power spectrum is present. We define an effective coupling to the environment that depends on all energy scales in the system and reservoir interaction. Sample computations in regimes predicted by this effective coupling are demonstrated. For example, for the case of strong effective coupling, deviations from standard thermodynamics are present and for the case of weak effective coupling, quantum features such as stationary entanglement are possible at high temperatures.
It is known that the origin of the deviations from standard thermodynamics proceed from the strong coupling to the bath. Here, it is shown that these deviations are related to the power spectrum of the bath. Specifically, it is shown that the system thermal-equilibrium-state cannot be characterized by the canonical Boltzmann's distribution in quantum mechanics. This is because the uncertainty principle imposed a lower bound of the dispersion of the total energy of the system that is dominated by the spectral density of the bath. However, in the classical case, for a wide class of systems that interact via central forces with pairwise-self-interacting environment, the system thermal equilibrium state is exactly characterized by the canonical Boltzmann distribution. As a consequence of this analysis and taking into account all energy scales in the system and reservoir interaction, an effective coupling to the environment is introduced. Sample computations in different regimes predicted by this effective coupling are shown. Specifically, in the strong coupling effective regime, the system exhibits deviations from standard thermodynamics and in the weak coupling effective regime, quantum features such as stationary entanglement are possible at high temperatures. Moreover, it is known that the spectrum of thermal baths depends on the non-Markovian character. Hence, non-Markovian interactions have a important role in the thermal equilibrium state of physical systems. For example, in quantum optomechanics is looked up to cool the mechanical system through an auxiliary system which generally is a cavity. This cooling process takes into account the non-Markovian interaction and as it is shown here, it is more effective than if we use only the Markovian approximation in the equation of motion for the different modes.
Thermodynamics typically concerns the physical behaviour of macroscopic systems comprised of many particles. However, recent theoretical progress has extended the theory to both the classical-stochastic and quantum regimes, where systems are comprised of just a small number of particles. In this thesis I investigate a range of situations in which new thermodynamic phenomena emerge due to the reduced size of the systems involved. One central assumption in macroscopic thermodynamics is the weak coupling approximation, which posits that the equilibrium properties of a system are not influenced by the interactions with its surrounding environment. However, for microscopic systems this assumption can break down, and I derive new fluctuation relations that provide a refined form of the second law of thermodynamics in this strong-coupling regime, taking into account corrections stemming from these interactions. In this work I provide a characterisation of stochastic heat and entropy production for small scale classical systems that are defined regardless of the strength of interaction. I then show that these definitions lead to a consistent thermodynamic framework valid beyond the usual weak-coupling regime. The thesis also concerns the effect of interactions on the equilibrium properties of strongly-coupled quantum systems, and I investigate how these interactions can influence the resulting temperature fluctuations in this regime. Using tools from quantum estimation theory, I derive an uncertainty relation between energy and temperature valid at all coupling strengths and system sizes. The relation reveals how quantum energy coherences contribute to statistical fluctuations in the estimated temperature of small- scale systems. Finally, I investigate how quantum fluctuations influence the statistics of work extracted from slowly-driven quantum systems. I prove that, unlike in classical systems, the work dissipated by a general quantum system is no longer proportional to its statistical fluctuations. This result reveals new subtleties involved in designing optimal quantum thermodynamic processes.
The Brownian motion of a quantum particle in a harmonic confining potential and coupled to harmonic quantum thermal bath is exactly solvable. Though this system presents at high temperatures a pedagogic example to explain the laws of thermodynamics, it is shown that at low enough temperatures the stationary state is non-Gibbsian due to an entanglement with the bath. In physical terms, this happens when the cloud of bath modes around the particle starts to play a nontrivial role, namely, when the bath temperature T is smaller than the coupling energy. Indeed, equilibrium thermodynamics of the total system, particle plus bath, does not imply standard equilibrium thermodynamics for the particle itself at low T. Various formulations of the second law are found to be invalid at low T. First, the Clausius inequality can be violated, because heat can be extracted from the zero point energy of the cloud of bath modes. Second, when the width of the confining potential is suddenly changed, there occurs a relaxation to equilibrium during which the entropy production is partly negative. In this process the energy put on the particle does not relax monotonically, but oscillates between particle and bath, even in the limit of strong damping. Third, for nonadiabatic changes of system parameters the rate of energy dissipation can be negative, and, out of equilibrium, cyclic processes are possible which extract work from the bath. Conditions are put forward under which perpetuum mobility of the second kind, having one or several work extraction cycles, enter the realm of condensed matter physics. Fourth, it follows that the equivalence between different formulations of the second law (e.g., those by Clausius and Thomson) can be violated at low temperatures. These effects are the consequence of quantum entanglement in the presence of the slightly off-equilibrium nature of the thermal bath, and become important when the characteristic quantum time scale variant Planck's over 2pi /k(B)T is larger than or comparable to other time scales of the system. They show that there is no general consensus between standard thermodynamics and quantum mechanics. The known agreements occur only due to the weak coupling limit, which does not pertain to low temperatures. Experimental setups for testing the effects are discussed.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
It is known that temperature estimates of macroscopic systems in equilibrium are most precise when their energy fluctuations are large. However, for nanoscale systems deviations from standard thermodynamics arise due to their interactions with the environment. Here we include such interactions and, using quantum estimation theory, derive a generalised thermodynamic uncertainty relation valid for classical and quantum systems at all coupling strengths. We show that the non-commutativity between the system's state and its effective energy operator gives rise to quantum fluctuations that increase the temperature uncertainty. Surprisingly, these additional fluctuations are described by the average Wigner-Yanase-Dyson skew information. We demonstrate that the temperature's signal-to-noise ratio is constrained by the heat capacity plus a dissipative term arising from the non-negligible interactions. These findings shed light on the interplay between classical and non-classical fluctuations in quantum thermodynamics and will inform the design of optimal nanoscale thermometers.