The photoelectron spectrum of the ethoxide anion: conical intersections, the spin-orbit interaction, and sequence bands.
The photoelectron spectrum of the ethoxide anion: conical intersections, the spin-orbit interaction, and sequence bands.
复制标题
乙醇阴离子的光电子能谱：圆锥形交叉点、自旋轨道相互作用和序列带。
DOI：
10.1063/1.3238155
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
D. Yarkony
中科院分区：
文献类型：
--
作者：
J. Dillon;D. Yarkony
用多模振子耦合方法计算了乙氧阴离子（乙氧-h（5））及其全氘代类似物乙氧-d（5）的负离子光电子能谱。本文构造了一个两态准绝热哈密顿量H（d），它包含了整个18维内坐标空间中的所有二阶项。H（d）的中心在从头算确定的最小能量交叉（MEX）点上，该点位于圆锥相交的随机允许的（2）A（“）-（2）A（”）偶然接缝上，并且由从头算能量梯度和导数耦合确定。它再现了（2）A（“）-（2）A（”）MEX的局部形貌，除了精确地表示位于MEX附近的基态电子态势能表面上的平衡和鞍点结构的几何形状、能量学和谐波频率之外。包括自旋轨道效应。乙氧基-h（5）的结果进行了比较，光电子和慢电子速度图成像（SEVI）光谱。通过比较光电子能谱的测量值和预测值，推测了电子结构处理的准确性。建立了SEVI谱中序列带的存在性。
The negative ion photoelectron spectrum of the ethoxide anion (ethoxide-h(5)) and that of its fully deuterated analog, ethoxide-d(5), are calculated using the multimode vibronic coupling approach. A two state quasidiabatic Hamiltonian H(d) is constructed which includes all terms through second order in the full 18 dimensional internal coordinate space. H(d) is centered at the ab initio determined minimum energy crossing (MEX) point on the symmetry-allowed (2)A(")-(2)A(') accidental seam of conical intersection and determined from ab initio energy gradients and derivative couplings. It reproduces the local topography of the (2)A(")-(2)A(') MEX, in addition to accurately representing the geometries, energetics, and harmonic frequencies of equilibrium and saddle point structures located on the ground electronic state potential energy surface in the vicinity of the MEX. Spin-orbit effects are included. The results for ethoxy-h(5) are compared to photoelectron and slow electron velocity-map imaging (SEVI) spectra. By comparing the measured and predicted photoelectron spectrum, the accuracy of the electronic structure treatment is inferred. The existence of sequence bands in the SEVI spectrum is established.