The Second Law of Thermodynamics places strictures on how systems can evolve over time. If we are to understand the fundamental nature of entropy in terms of the microscopic world, its relationship to the Second Law forces us to consider how quantum systems progress with time. It appears at first glance that the unitary time evolution characteristic of the Schrödinger equation conflicts with the Second Law. Resolving this issue will cast new perspective on the nature of entropy .
The Second Law of Thermodynamics places strictures on how systems can evolve over time. If we are to understand the fundamental nature of entropy in terms of the microscopic world, its relationship to the Second Law forces us to consider how quantum systems progress with time. It appears at first glance that the unitary time evolution characteristic of the Schrödinger equation conflicts with the Second Law. Resolving this issue will cast new perspective on the nature of entropy .
The second law of thermodynamics states that the entropy of an isolated system can only increase over time. This appears to conflict with the reversible evolution of isolated quantum systems under the Schrödinger equation, which preserves the von Neumann entropy. Nonetheless, one finds that with respect to many observables, expectation values approach a fixed value—their equilibrium value. This ultimately raises the question: ? For classical systems, one introduces the assumption of a low-entropy initial state along with the concept of ignorance about the microscopic details of the physical system, leading to a statistical interpretation of the second law. By considering the observables through which we examine quantum systems, both these assumptions can be incorporated, building upon recent studies of the of observables. While the statistical behavior of observable expectation values is well established, a quantitative connection to entropy increase has been lacking so far. In deriving novel bounds for the equilibration of observables, and considering the entropy of the system relative to observables, we recover a variant of the second law: the entropy with respect to a given observable tends toward its equilibrium value in the course of the system’s unitary evolution. These results also support recent findings that question the necessity of nonintegrability for equilibration in quantum systems. We further illustrate our bounds using numerical results from the paradigmatic example of a quantum Ising model on a chain of spins. There, we observe entropy increasing up to equilibrium values, as well as fluctuations, which expose the underlying reversible evolution in accordance with the derived bounds.
For a quantum state undergoing unitary Schrödinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator [R. S. Ingarden, Quantum information theory, Rep. Math. Phys. 10, 43 (1976)RMHPBE0034-487710.1016/0034-4877(76)90005-7]. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system composed of a set of highly interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.
For a quantum state undergoing unitary Schrodinger time evolution, the von Neumann entropy is constant. Yet the second law of thermodynamics, and our experience, show that entropy increases with time. Ingarden introduced the quantum operator entropy, which is the Shannon entropy of the probability distribution for the eigenvalues of a Hermitian operator. These entropies characterize the missing information about a particular observable inherent in the quantum state itself. The von Neumann entropy is the quantum operator entropy for the case when the operator is the density matrix. We examine pure state unitary evolution in a simple model system comprised of a set of highly-interconnected topologically disordered states and a time-independent Hamiltonian. An initially confined state is subject to free expansion into available states. The time development is completely reversible with no loss of quantum information and no course graining is applied. The positional entropy increases in time in a way that is consistent with both the classical statistical mechanical entropy and the second law.
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.
All the laws of physics are time-reversible. Time arrow emerges only when ensembles of classical particles are treated probabilistically, outside of physics laws, and the entropy and the second law of thermodynamics are introduced. In quantum physics, no mechanism for a time arrow has been proposed despite its intrinsic probabilistic nature. In consequence, one cannot explain why an electron in an excited state will "spontaneously" transition into a ground state as a photon is created and emitted, instead of continuing in its reversible unitary evolution. To address such phenomena, we introduce an entropy for quantum physics, which will conduce to the emergence of a time arrow. The entropy is a measure of randomness over the degrees of freedom of a quantum state. It is dimensionless; it is a relativistic scalar, it is invariant under coordinate transformation of position and momentum that maintain conjugate properties and under CPT transformations; and its minimum is positive due to the uncertainty principle. To excogitate why some quantum physical processes cannot take place even though they obey conservation laws, we partition the set of all evolutions of an initial state into four blocks, based on whether the entropy is (i) increasing but not a constant, (ii) decreasing but not a constant, (iii) a constant, (iv) oscillating. We propose a law that in quantum physics entropy (weakly) increases over time. Thus, evolutions in the set (ii) are disallowed, and evolutions in set (iv) are barred from completing an oscillation period by instantaneously transitioning to a new state. This law for quantum physics limits physical scenarios beyond conservation laws, providing causality reasoning by defining a time arrow.
This work investigates the fundamental connection between quantum mechanics and thermodynamics through the concept of the arrow of time. While the second law of thermodynamics identifies the arrow of time with the monotonic increase of entropy in isolated systems, closed quantum systems evolve unitarily and conserve von Neumann entropy, making the origin of irreversibility less apparent. Here we establish a no-go theorem proving that correlations in unknown states of closed quantum systems cannot be universally removed by any physical operation. This result demonstrates that correlation generation is inherently irreversible, providing a microscopic and universal basis for the arrow of time. In thermodynamic settings, this irreversibility ensures that heat flows spontaneously from hotter to colder subsystems, reproducing the Clausius formulation of the second law. More generally, the irreversible growth of correlations explains entropy increase, the approach to equilibrium, and decoherence as observable manifestations of the same principle. Our findings ground a quantum-mechanical foundation for the second law of thermodynamics and demonstrate the universality of the arrow of time.