We construct a finite bath with variable temperature for quantum thermodynamic simulations in which heat flows between a system S and the bath environment E in time evolution of an initial SE pure state. The bath consists of harmonic oscillators that are not necessarily identical. Baths of various numbers of oscillators are considered; a bath with five oscillators is used in the simulations. The bath has a temperaturelike level distribution. This leads to definition of a system-environment microcanonical temperature T_{SE}(t) which varies with time. The quantum state evolves toward an equilibrium state which is thermal-like, but there is significant deviation from the ordinary energy-temperature relation that holds for an infinite quantum bath, e.g., an infinite system of identical oscillators. There are also deviations from the Einstein quantum heat capacity. The temperature of the finite bath is systematically greater for a given energy than the infinite bath temperature, and asymptotically approaches the latter as the number of oscillators increases. It is suggested that realizations of these finite-size effects may be attained in computational and experimental dynamics of small molecules.
We construct a finite bath with variable temperature for quantum thermodynamic simulations in which heat flows between a system S and the bath environment E in time evolution of an initial SE pure state. The bath consists of harmonic oscillators that are not necessarily identical. Baths of various numbers of oscillators are considered; a bath with five oscillators is used in the simulations. The bath has a temperaturelike level distribution. This leads to definition of a system-environment microcanonical temperature T_{SE}(t) which varies with time. The quantum state evolves toward an equilibrium state which is thermal-like, but there is significant deviation from the ordinary energy-temperature relation that holds for an infinite quantum bath, e.g., an infinite system of identical oscillators. There are also deviations from the Einstein quantum heat capacity. The temperature of the finite bath is systematically greater for a given energy than the infinite bath temperature, and asymptotically approaches the latter as the number of oscillators increases. It is suggested that realizations of these finite-size effects may be attained in computational and experimental dynamics of small molecules.
Simulations are performed of a small quantum system interacting with a quantum environment. The system consists of various initial states of two harmonic oscillators coupled to give normal modes. The environment is "designed" by its level pattern to have a thermodynamic temperature. A random coupling causes the system and environment to become entangled in the course of time evolution. The approach to a Boltzmann distribution is observed, and effective fitted temperatures close to the designed temperature are obtained. All initial pure states of the system are driven to equilibrium at very similar rates, with quick loss of memory of the initial state. The time evolution of the von Neumann entropy is calculated as a measure of equilibration and of quantum coherence. It is pointed out using spatial density distribution plots that quantum interference is eliminated only with maximal entropy, which corresponds thermally to infinite temperature. Implications of our results for the notion of "classicalizing" behavior in the approach to thermal equilibrium are briefly considered.
A model computational quantum thermodynamic network is constructed with two variable temperature baths coupled by a linker system, with an asymmetry in the coupling of the linker to the two baths. It is found in computational simulations that the baths come to "thermal equilibrium" at different bath energies and temperatures. In a sense, heat is observed to flow from cold to hot. A description is given in which a recently defined quantum entropy S_{univ}^{Q} for a pure state "universe" continues to increase after passing through the classical equilibrium point of equal temperatures, reaching a maximum at the asymmetric equilibrium. Thus, a second law account ΔS_{univ}^{Q}≥0 holds for the asymmetric quantum process. In contrast, a von Neumann entropy description fails to uphold the entropy law, with a maximum near when the two temperatures are equal, then a decrease ΔS^{vN}<0 on the way to the asymmetric equilibrium.
Recent theoretical and experimental work on the foundations of statistical mechanics and thermodynamics has shown that quantum pure states typically evolve to thermal equilibrium. We focus on formulating the second law of thermodynamics for these states. The standard quantum von Neumann quantum entropy is constant during equilibration, S^{vN}=0, in apparent conflict with the entropy increase of the second law, ΔS_{univ} > 0. We explore a recently developed entropy S_{univ}^Q for a pure state and test its behavior in simulations of a model system and environment evolving in time with heat flow to equilibrium. We find that the entropy approaches the correct classical value in a type of classical limit with weak coupling. With stronger coupling, we find a new source of quantum "excess entropy production," which has its origin in the quantum spreading of the wavepacket. Are there quantum thermodynamic effects related to this new source of entropy? To test this, we developed a model for a small variable temperature quantum oscillator bath. We performed simulations where two small baths are linked by a system, with unequal couplings to the baths. The model evolves to a novel type of equilibrium state with unequal temperatures in the baths, with heat flow from cold to hot along the path to equilibrium. We give an account of this behavior in terms of the second law with the quantum entropy S_{univ}^Q. The new formulation of the second law thus appears well-founded and fruitful, with surprising new quantum thermodynamic effects that may still be awaiting discovery, for example in molecules or systems far from equilibrium. \n\nThis dissertation includes previously published and unpublished co-authored material.
We consider a situation where an N-level system (NLS) is coupled successively to two heat baths with different temperatures without being necessarily thermalized and approaches a steady state. For this situation we apply a general Jarzinski-type equation and conclude that heat and entropy is flowing from the hot bath to the cold one. The Clausius relation between increase of entropy and transfer of heat divided by a suitable temperature assumes the form of two inequalities. Our approach is illustrated by an analytical example. For the linear regime, i.~e., for small temperature differences between the two heat baths we derive an expression for the heat conduction coefficient.
The prevailing method for addressing strong-coupling thermodynamics typically involves open quantum systems coupled to infinite baths in equilibrium through the Hamiltonian of mean force (HMF). However, its applicability to finite baths remains limited. In this work, we transcend this limit by considering the impacts of system-bath coupling which is not only on the system but also on the finite bath feedback. When the bath and system sizes are comparable, they act as each other's effective 'bath'. We introduce a parameter α within [0,1], where α and 1-α act as weighting factors to distribute the system-bath coupling between the system and the bath. Our approach innovatively incorporates the effect of coupling on the respective effective 'bath' into both the system and bath in the statistical factor form. We generalize the HMF and propose quantum Hamiltonians of mean forces to handle the distributed coupling of the system to finite baths. The additional parameter α is determined by minimizing the joint free energy density and is a new thermodynamic quantity representing the finite bath's influence. Examining the damped quantum harmonic oscillator with a finite bath, we find that α affects both states, leading to a complex phase diagram with unique phenomena at critical temperatures T_{L} and T_{R}, including valleys, peaks, negative values, and discontinuities in entropy and specific heat. Notably, these anomalies disappear when α→1, both at high temperatures and in the thermodynamic limit, indicating the negligible influence of coupling on the bath states and reverting to the HMF. Thus, studying finite-sized baths holds substantial significance in small quantum systems.
For a small system at a low temperature, thermal fluctuation and quantum effect play important roles in quantum thermodynamics. Starting from micro-canonical ensemble, we generalize the Boltzmann–Gibbs statistical factor from infinite to finite systems, no matter the interactions between particles are considered or not. This generalized factor, similar to Tsallis’s q-form as a power-law distribution, has the restriction of finite energy spectrum and includes the nonextensivities of the small systems. We derive the exact expression for distribution of average particle numbers in the interacting classical and quantum nonextensive systems within a generalized canonical ensemble. This expression in the almost independent or elementary excitation quantum finite systems is similar to the corresponding ones obtained from the conventional grand-canonical ensemble. In the reconstruction for the statistical theory of the small systems, we present the entropy of the equilibrium systems and equation of total thermal energy. When we investigate the thermodynamics for the interacting nonextensive systems, we obtain the system–bath heat exchange and “uncompensated heat” which are in the thermodynamical level and independent on the detail of the system–bath coupling. For ideal finite systems, with different traps and boundary conditions, we calculate some thermodynamic quantities, such as the specific heat, entropy, and equation of state, etc. Particularly at low temperatures for the small systems, we predict some novel behaviors in the quantum thermodynamics, including internal entropy production, heat exchanges between the system and its surroundings and finite-size effects on the free energy.