Analysis of the HO2 Vibrational Spectrum on an Accurate Ab Initio Potential Energy Surface

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• 作者：Chuanxiu Xu ; Bin Jiang ; Daiqian Xie ; Stavros C. Farantos ; Shi Ying Lin ; Hua Guo
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：October 18, 2007
• 年：2007
• 卷：111
• 期：41
• 页码：10353 - 10361
• 全文大小：481K
• 年卷期：v.111,no.41(October 18, 2007)
• ISSN：1520-5215

文摘

The complete vibrational spectrum of the HO₂(²A' ') radical, up to the H + O₂ dissociation limit, has beendetermined quantum mechanically on an accurate potential energy surface (PES), based on ~15000 ab initiopoints at the icMRCI+Q/aug-cc-pVQZ level of theory. The vibrational states are found to be assignable atlow energies but become more irregular as the energy approaches the dissociation limit. However, even atvery high energies, regularity still exists, in sharp contrast to earlier results based on the double many-bodyexpansion (DMBE) IV potential. Several Fermi resonances have been identified, and the spectrum is fit witha spectroscopic Hamiltonian. In addition, the vibrational dynamics is analyzed using a periodic orbit approach.