A (2)A(2)<--X (2)B(1) absorption and Raman spectra of the OClO molecule: a three-dimensional time-dependent wave packet study.
Time-dependent wave packet calculations of the (A (2)A(2)<--X (2)B(1)) absorption and Raman spectra of the OClO molecule are reported. The Fourier grid Hamiltonian method in three dimensions is employed. The X (2)B(1) ground state ab initio potential energy surface reported by Peterson is used together with his corresponding A (2)A(2) state surface or the revised surface of the A (2)A(2) state by Xie and Guo. Radau coordinates are used to describe the vibrations of a nonrotating OClO molecule. The split-operator method combined with fast Fourier transform is applied to propagate the wave function. We find that the ab initio A (2)A(2) potential energy surface better reproduces the detailed structures of the absorption spectrum at long wavelength, while the revised surface of the A (2)A(2) state, consistent with the work of Xie and Guo, better reproduces the overall shape and the energies of the vibrational levels. Both surfaces of the A (2)A(2) state can reasonably reproduce the experimental Raman spectra but neither does so in detail for the numerical model employed in the present work.
Sun
Zhigang
Z
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of ChinaGraduate School of Chinese Academy of Sciences, Dalian 116023, People's Republic of China. zsun@dicp.ac.cn
Lou
Nanquan
N
Nyman
Gunnar
G