Vibrational Dynamics of the CH4路F鈥?/sup>Complex

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• 作者：Robert Wodraszka ; Juliana Palma ; Uwe Manthe
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：November 26, 2012
• 年：2012
• 卷：116
• 期：46
• 页码：11249-11259
• 全文大小：427K
• 年卷期：v.116,no.46(November 26, 2012)
• ISSN：1520-5215

文摘

Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH₄ 鈫?HF + CH₃ reaction, the vibrational dynamics of the precursor complex CH₄路F^{鈥?/sup> is investigated. Delocalized vibrational eigenstates of CH₄路F鈥?/sup> are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH₄路F鈥?/sup> complex do not significantly exceed 1 cm鈥?. Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes.}