a Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, 1 Section 4, Roosevelt Road Taipei 106, Taiwan ROC
Abstract:
The structures and vibrations of p-diaminobenzene (PDAB) in the S0 and S1 states have been studied by ab initio quantum-chemical calculations. Results from geometry optimization show that the two stable cis and trans conformers of PDAB are non-planar in the S0 state. Upon electronic excitation to the S1 state, enhanced interaction between the ring and the amino substituent causes the molecule to become planar and contract along the long in-plane axis. A detailed analysis of the normal vibrations of PDAB in both states has been done on the basis of the motions of individual atoms as well as reduced masses, force constants and frequencies. The computed frequencies are in reasonably good agreement with the available experimental data.