Efficient non-resonant intermolecular vibrational energy transfer

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 neighbouring molecule are derived in closed form. These expressions allow one to analyse 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.

GRAPHICAL ABSTRACT

Keywords:

• Vibrational energy transfer
• non-resonant energy transfer
• interacting resonances

Acknowledgments

The author thanks I. Baldea, S. Klaiman, A. Kuleff, R. Marquardt, M. Quack and P. Saalfrank for valuable contributions.

Disclosure statement

No potential conflict of interest was reported by the author.

Additional information

Funding

Financial support by the Deutsche Forschungsgemeinschaft DFG ( research unit 1789) and by the European Research Council (ERC) (Advanced Investigator Grant No. 692657) is gratefully acknowledged.