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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Complex dynamics at conical intersections: Vibronic spectra and ultrafast decay of electronically excited trifluoroacetonitrile radical cation
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Complex dynamics at conical intersections: Vibronic spectra and ultrafast decay of electronically excited trifluoroacetonitrile radical cation

机译：圆锥形交叉点的复杂动力学：电子激发的三氟乙腈自由基阳离子的电子能谱和超快衰减

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摘要

An ab initio quantum dynamical study is performed here to examine the complex nuclear motion underlying the first two photoelectron bands of trifluoroacetonitrile. The highly overlapping structures of the latter are found to originate from transitions to the five lowest electronic states (viz., (X) over tilde E-2, (A) over tilde (2)A(1), (B) over tilde (2)A(2), (C) over tilde (2)A(1), and (D) over tilde E-2 of the trifluoroacetonitrile radical cation. The Jahn-Teller (JT) instability of the doubly degenerate (X) over tilde and, (D) over tilde and their pseudo-Jahn-Teller (PJT) interactions with the nondegenerate (A) over tilde, (B) over tilde, and (C) over tilde electronic states along the degenerate vibrational modes lead to multiple multidimensional conical intersections and complex nuclear trajectories through them. It is found that the JT splitting is very weak in the (X) over tilde and relatively stronger in the (D) over tilde state. However, the PJT couplings play the pivotal role in the detailed shape of the vibronic bands of the radical cation. Ultrafasst nonradiative decay of electronically excited radical cation has been examined. The findings of this paper dire compared with the experimental data and are also discussed in relation to those observed for the methyl cyanide radical cation.
机译：从头进行量子动力学研究，以检查在三氟乙腈的前两个光电子带之下的复杂核运动。发现后者的高度重叠结构源自过渡到五个最低电子状态（即，在波浪号E-2上为（X），在波浪号上为（A）（在波浪号上为（2）A（1），在波浪号上为（B）） （2）A（2），（C）于代字号（2）A（1）和（D）于代字号E-2上的三氟乙腈自由基阳离子。双简并列式（X ）上的波浪线，（D）上的波浪线以及它们与非简并（A）的波浪线之间的伪Jahn-Teller（PJT）相互作用，（B）的波浪线上方，以及（C）沿着简并的振动模态的波浪线电子态通过多个多维圆锥形交叉点和复杂的核轨迹，发现JT分裂在波浪线的（X）上非常弱，而在（D）波浪线的JD上相对较强，但是PJT耦合起着关键作用根据自由基阳离子的振动带的详细形状，研究了电子激发自由基阳离子的超快非辐射衰变。本文的意图与实验数据进行了比较，并就所观察到的甲基氰化物自由基阳离子进行了讨论。

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