Efficient non-resonant intermolecular vibrational energy transfer

TL;DR

This paper develops a theoretical framework for vibrational energy transfer between weakly interacting molecules, highlighting how finite lifetimes enable efficient off-resonance energy transfer.

Contribution

It introduces closed-form expressions for effective vibrational lifetimes considering neighboring molecules, advancing understanding of non-resonant energy transfer mechanisms.

Findings

Efficient energy transfer occurs even off-resonance due to finite lifetimes.

Derived formulas enable analysis of vibrational energy transfer physics.

Examples demonstrate the theory's applicability.

Abstract

Molecular excited vibrational states are metastable states and we incorporate their finite lifetimes into the theory of vibrational energy transfer between weakly interacting molecules, i.e., at internuclear distances at which they do not have a chemical bond. Expressions for the effective lifetime of an initially vibrationally excited molecule in the presence of a neighboring molecule are derived in closed form. These expressions allow one to analyze the physics behind the energy transfer. It is shown that due to different finite lifetimes of the isolated excited molecules, a very efficient vibrational energy transfer can take place between them even if their energies are rather off-resonance. Examples are discussed.