Biological and Chemical Physics


Global three dimensional potential energy surfaces and transition dipole moment functions are calculated for the lowest singlet and triplet states of carbonyl sulfide at the multireference configuration interaction level of theory. The first ultraviolet absorption band is then studied by means of quantum mechanical wave packet propagation. excitation of the repulsive 21A' state gives the main contribution to the cross section. Excitation of the repulsive 11A" state is about a factor of 20 weaker at the absorption peak (Eph ≈ 45 000 cm-1) but becomes comparable to the 21A' state absorption with decreasing energy (35 000 cm-1) and eventually exceeds it. Direct excitation of the repulsive triplet states is negligible except at photon energies Eph < 38 000 cm-1. The main structure observed in the cross section is caused by excitation of the bound 23A" state, which is nearly degerate with the 2 1A' state in the Franck-Condon region. The structure observed in the low energy tail of the spectrum is caused by excitation of quasi-bound bending vibrational states of the 21A' and 11A" electronic states. The absorption cross sections agree well with experimental data and the temperature dependence of the cross section is well reproduced.


Original Citation: J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke. ¿e ultraviolet spectrum of OCS from first principles: Electronic transitions, vibrational structure and temperature dependence. J. Chem. Phys., 137(5):054313, 2012.