Donor's position-specific channel interference in substituted biphenyl molecules

Abstract

The channel interference mechanism describes the two-photon absorption process in terms of the relative orientations of different transition dipole moment vectors (TDMVs) in a molecule. Controlling these interferences is a difficult but important task, because it can provide new information about such absorption/emission processes. The present contribution aims to explain the reversal in the nature of these interferences with the relative positions of the donor–acceptor groups in substituted biphenyl molecules. The results obtained from the linear and quadratic response theories indicate that having the donor at the para position leads to a constructive interference whereas having it at any of the other two positions results in a destructive interference. This is explained by a systematic analysis of the relative orientations of all the TDMVs involved in a three-state model.