Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state.
Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state.
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DOI：
10.1063/1.4931918
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发表时间：
2015-10
期刊：
影响因子：
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通讯作者：
F. Morini;N. Watanabe;M. Kojima;M. Deleuze;M. Takahashi
中科院分区：
文献类型：
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作者：
F. Morini;N. Watanabe;M. Kojima;M. Deleuze;M. Takahashi
用谐波分析量子力学和Born-Oppenheimer分子动力学方法研究了二甲醚分子基态核动力学对（e，2 e）动量分布的影响.尽管基本方法的差异，用这两种方法得到的结果一致表明，在电子基态的分子振动有一个最明显的影响与2b 1，6a 1，4 b2和1a 2轨道的动量分布。考虑到这种影响，大大提高了理论和新获得的实验动量分布之间的协议，提高了统计精度。这两种方法都特别指出了A1、B1和B2对称性的一些特定分子振动所起的最明显的作用，这些振动对应于C-H伸缩和H-C-H弯曲模式。根据Herzberg-Teller原理，这些分子振动对计算的动量分布的影响可以从考虑轨道的对称性及其能量间隔来解释。
The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b1, 6a1, 4b2, and 1a2 orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A1, B1, and B2 symmetries, which correspond to C-H stretching and H-C-H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.