Density functional study on the circular dichroism of photoelectron angular distribution from chiral derivatives of oxirane.
Density functional study on the circular dichroism of photoelectron angular distribution from chiral derivatives of oxirane.
复制标题
环氧乙烷手性衍生物光电子角分布圆二色性的密度泛函研究。
DOI：
10.1063/1.1640617
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
P. Decleva
中科院分区：
文献类型：
--
作者：
M. Stener;G. Fronzoni;D. Tommaso;P. Decleva
原子轨道的线性组合B - 样条密度泛函方法已成功应用于一系列四种环氧乙烷的手性衍生物，用于计算光电离动力学参数、角分布效应中的圆二色性，并确定该系列中的趋势。计算算法已证明在数值上稳定且具有计算竞争力。对于在该系列中保持其性质的态，已系统地研究了相对于价轨道的光电离截面、不对称性和二色性参数分布：所确定的趋势归因于取代基的不同电子性质。在许多情况下，发现二色性参数对电子结构变化具有相当出乎意料的敏感性，这使得这种动力学性质适合用于研究手性化合物的电子结构。角分布效应中圆二色性的大小似乎与初始态的手性无关，而是由离域光电子波函数探测分子有效势不对称性的能力所决定。
The linear combination of atomic orbitals B-spline density functional method has been successfully applied to a series of four chiral derivatives of oxirane, to calculate the photoionization dynamical parameters, the circular dichroism in the angular distribution effect, and to identify trends along the series. The computational algorithm has proven numerically stable and computationally competitive. The photoionization cross section, asymmetry, and dichroic parameter profiles relative to valence orbitals have been systematically studied for the states which retain their nature along the series: the identified trends have been ascribed to the different electronic properties of the substituents. A rather unexpected sensitivity of the dichroic parameter to changes in the electronic structure has been found in many instances, making this dynamical property suitable to investigate the electronic structure of chiral compounds. The magnitude of the circular dichroism in the angular distribution effect does not seem to be associated with the initial state chirality, but rather to be governed by the ability of the delocalized photoelectron wave function to probe the asymmetry of the molecular effective potential.