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A (2)A(2)<--X (2)B(1) absorption and Raman spectra of the OClO molecule: a three-dimensional time-dependent wave
Zhigang Sun1, Nanquan Lou, Gunnar Nyman
1Dalian 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
Abstract:
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.
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