Stener M, Di Tommaso D, Fronzoni G, Decleva P, Powis I
Dipartimento di Scienze Chimiche, Università di Trieste, Via Licio Giorgieri 1, I-34127 Trieste, Italy.
J Chem Phys. 2006 Jan 14;124(2):024326. doi: 10.1063/1.2150438.
In the present work the photoelectron circular dichroism of camphor has been theoretically studied using B-spline and continuum multiple scattering-Xalpha methods, and comparisons are made with available experimental data. In general, rather large dichroism effects have been found for both valence and core (O 1s, C 1s) photoionizations. The agreement between the two calculations reported here and previous experimental measurements for core C 1s data is essentially quantitative. For valence ionization satisfactory agreement between theory and experiment has been obtained and the discrepancies have been attributed to both exchange-correlation potential limitations and the absence of response effects in the adopted formalism. The calculations predict, moreover, important features in the cross-section profiles, which have been discussed in terms of dipole-prepared continuum orbitals.
在本工作中，利用B样条和连续介质多重散射-Xα方法对樟脑的光电子圆二色性进行了理论研究，并与现有的实验数据进行了比较。总体而言，已发现价态和内层（O 1s、C 1s）光电离均存在相当大的二色性效应。此处报道的两种计算结果与先前关于内层C 1s数据的实验测量结果在本质上是定量相符的。对于价态电离，理论与实验已获得令人满意的相符结果，差异归因于交换关联势的局限性以及所采用形式体系中响应效应的缺失。此外，计算预测了截面轮廓中的重要特征，这些特征已根据偶极制备的连续轨道进行了讨论。
