Ab Initio Quantum Mechanical Study of the O(1D) Formation in the Photolysis of Ozone between 300 and 330 nm
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- 作者：Sergy Yu. Grebenshchikov ; Salman Rosenwaks
- 刊名：Journal of Physical Chemistry A
- 出版年：2010
- 出版时间：September 16, 2010
- 年：2010
- 卷：114
- 期：36
- 页码：9809-9819
- 全文大小：441K
- 年卷期：v.114,no.36(September 16, 2010)
- ISSN：1520-5215
文摘
Spin-allowed production of O(1D) in the near-UV photolysis of ozone is studied using ab initio potential energy surfaces and quantum mechanics. The O(1D) quantum yield, reconstructed from the absolute cross sections for eight initial vibrational states in the ground electronic state, is shown to agree with the measurements in a broad range of photolysis wavelengths and temperatures. Relative contributions of one- and two-quantum stretching and bending initial excitations are quantified, with the contribution of the antisymmetric stretch being dominant for λ < 330 nm. Large scale structures in the low-resolution quantum yield are shown to reflect excitations in the high-frequency short bond stretch in the upper electronic state. Spin-forbidden contribution to the O(1D) quantum yield at wavelengths λ > 320 nm is estimated using ab initio energies of the triplet states and their spin−orbit couplings.