Non-Markovian theory of vibrational energy relaxation and its applications to biomolecular systems

TL;DR

This paper develops a non-Markovian theoretical framework for vibrational energy relaxation in biomolecular systems, incorporating anharmonic mode coupling and atomistic detail, to better understand energy transfer mechanisms at microscopic timescales.

Contribution

It introduces a non-Markovian VER formula derived from a reduced normal mode model with anharmonic coupling, applicable to biomolecular systems at sub-picosecond timescales.

Findings

VER timescales and mechanisms analyzed in biomolecules

Application of formulas to peptide, porphyrin, and protein systems

Comparison with experimental data where available

Abstract

Energy transfer (relaxation) phenomena are ubiquitous in nature. At a macroscopic level, the phenomenological theory of heat (Fourier law) successfully describes heat transfer and energy flow. However, its microscopic origin is still under debate. This is because the phenomena can contain many-body, multi-scale, nonequilibrium, and even quantum mechanical aspects, which present significant challenges to theories addressing energy transfer phenomena in physics, chemistry and biology. In this paper, we describe our recent theoretical attempts to treat vibrational energy relaxation (VER) in biomolecular systems, including peptide, porphyrin, and protein. First we construct a reduced model using (instantaneous) normal mode analysis, and further add anharmonic coupling between vibrational modes. Using such a model combined with time-dependent perturbation theory for the anharmonic coupling, we derive non-Markovian VER formulas, which are applicable to small timescales such as sub picoseconds. We apply the VER formulas with full atomistic detail to various biomolecular systems, discuss the VER timescales and mechanisms, and compare with experiment if possible. We finally mention further theoretical prospects of the energy transfer phenomena in physics, chemistry, and biology.