化学
偶极子
计算化学
从头算
激发态
吲哚试验
从头算量子化学方法
发色团
电子结构
加法函数
分子物理学
分子几何学
分子轨道
原子物理学
分子
立体化学
光化学
物理
有机化学
数学
数学分析
作者
Josefin Wilke,Martin Wilke,Christian Brand,W. Leo Meerts,Michaël Schmitt
出处
期刊:ChemPhysChem
[Wiley]
日期:2016-06-01
卷期号:17 (17): 2736-2743
被引量:16
标识
DOI:10.1002/cphc.201600420
摘要
The estimate of the magnitude and the orientation of molecular electric dipole moments from the vector sum of bond or fragment dipole moments is a widely used approach in chemistry. However, the limitations of this intuitive model have rarely been tested experimentally, particularly for electronically excited states. Herein, we find rules for a number of indole derivatives by using rotationally resolved electronic Stark spectroscopy and ab initio calculations. Based on a natural-bond-orbital analysis, we discuss whether the vector additivity rule can be applied in a given electronic state. From a comparison of the experimental data with ab initio calculations, we deduced that the additivity model does not apply when the flow of electron density from the substituent is opposed to that inside the chromophore.
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