Influence of non-Markovian dynamics in equilibrium uncertainty-relations

J Chem Phys. 2019 Jan 21;150(3):034105. doi: 10.1063/1.5055061.

Abstract

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.