Quantum mechanical tunnelling in the radiationless transitions of large molecules

Abstract

A theory, based on a quantum mechanical tunnelling process in the potential surfaces of the CH stretching modes, is used to interpret non-radiative transitions in aromatic compounds. The model gives absolute rate constants in agreement with experiment, leads to good correlations of non-radiative transition rates with the electronic energy of the excited states, accounts for temperature and solvent effects and provides a good quantitative description of the variation of the non-radiative rate with the increase of the vibrational energy content of the molecules.