Curl flux, coherence, and population landscape of molecular systems: Nonequilibrium quantum steady state, energy (charge) transport, and thermodynamics

TL;DR

This paper develops a theoretical framework for analyzing non-equilibrium quantum steady states in molecular systems, linking curl flux, coherence, and thermodynamics to energy and charge transport properties.

Contribution

It introduces an analytical approach connecting curl quantum flux, coherence, and thermodynamics in non-equilibrium molecular quantum systems, with validation against experimental data.

Findings

Quantum flux relates to non-equilibrium driving and tunneling.

Coherence enhances flux at low tunneling, reduces it at high tunneling.

High voltage achieves near-perfect chemical reaction efficiency.

Abstract

We established a theoretical framework in terms of the curl flux, population landscape, and coherence for non-equilibrium quantum systems at steady state, through exploring the energy and charge transport in molecular processes. The curl quantum flux plays the key role in determining transport properties and the system reaches equilibrium when flux vanishes. The novel curl quantum flux reflects the degree of non-equilibriumness and the time-irreversibility. We found an analytical expression for the quantum flux and its relationship to the environmental pumping (non-equilibriumness quantified by the voltage away from the equilibrium) and the quantum tunneling. Furthermore, we investigated another quantum signature, the coherence, quantitatively measured by the non-zero off diagonal element of the density matrix. Besides the environment-assistance which can give dramatic enhancement of coherence and quantum flux with high voltage at a fixed tunneling strength, the quantum flux is promoted by the coherence in the regime of small tunneling while reduced by the coherence in the regime of large tunneling, due to the non-monotonic relationship between the coherence and tunneling. In view of the system as a quantum heat engine, we studied the non-equilibrium thermodynamics and established the analytical connections of curl quantum flux to the transport quantities such as energy (charge) transfer efficiency, chemical reaction efficiency, energy dissipation, heat and electric currents observed in the experiments. We observed a perfect transfer efficiency in chemical reactions at high voltage (chemical potential difference). Our theoretical predicted behavior of the electric current with respect to the voltage is in good agreements with the recent experiments on electron transfer in single molecules.