Energy, Work, Entropy, and Heat Balance in Marcus Molecular Junctions.

We present a consistent theory of energy balance and conversion in a single-molecule junction with strong interactions between electrons on the molecular linker (dot) and phonons in the nuclear environment where the Marcus-type electron hopping processes predominate in the electron transport. It is shown that the environmental reorganization and relaxation that accompany electron hopping energy exchange between the electrodes and the nuclear (molecular and solvent) environment may bring a moderate local cooling of the latter in biased systems. The effect of a periodically driven dot level on the heat transport and power generated in the system is analyzed, and energy conservation is demonstrated both within and beyond the quasistatic regime. Finally, a simple model of atomic scale engine based on a Marcus single-molecule junction with a driven electron level is suggested and discussed.