Montuoro Raffaele, Lucchese Robert R, Bozek John D, Das Aloke, Poliakoff E D
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
J Chem Phys. 2007 Jun 28;126(24):244309. doi: 10.1063/1.2743430.
The authors report a fully vibrationally resolved photoelectron spectroscopy investigation of a nonplanar molecule studied over a range of excitation energies. Experimental results for all four fundamental vibrational modes are presented. In each case significant non-Franck-Condon effects are seen. The vibrational branching ratio for the totally symmetric mode nu1+ is found to be strongly affected by resonant excitation in the SiF4+ (D2A1) photoionization channel. This is shown to be the result of two distinct shape resonances, which for the first time have been both confirmed by theoretical calculations. Vibrationally resolved Schwinger photoionization calculations are used to understand the vibronic coupling for the photoelectrons, both using ab initio and harmonic vibrational wave functions.
作者报告了对一个非平面分子在一系列激发能量下进行的全振动分辨光电子能谱研究。给出了所有四种基本振动模式的实验结果。在每种情况下都观察到了显著的非弗兰克 - 康登效应。发现全对称模式ν1 + 的振动分支比在SiF4 + （D2A1）光电离通道中受到共振激发的强烈影响。这被证明是两个不同形状共振的结果，这两个共振首次都通过理论计算得到了证实。使用振动分辨的施温格光电离计算来理解光电子的振动 - 电子耦合，同时使用从头算和谐波振动波函数。
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