LIF excitation spectra of o- and m-cyanoanilines

Abstract

LIF excitation spectra of 2-cyanoaniline (2-CA) and 3-cyanoaniline (3-CA) in their hydrogen (–NH₂) and deuterium (–ND₂) forms are presented and discussed. Analyses of harmonic motions for the three mono cyanoanilines are presented, using the results of ab initio (HF/6-31++G^** and CIS/6-31++G^**) quantum mechanical calculations for ground and excited electronic states, as well as IR and Raman frequencies. Previous assignments of IR and Raman spectra of the cyanoanilines are compared with the ab initio calculations. Potential energy changes upon electronic excitation, to the lowest singlet state, for the cyanoanilines are interpreted in terms of harmonic frequencies, displacements of normal modes and Dushinsky rotation matrices.