Density functional theory calculation of electronic circular dichroism using London orbitals
Density functional theory calculation of electronic circular dichroism using London orbitals
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DOI：
10.1016/j.cplett.2004.03.008
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发表时间：
2004-04-11
影响因子：
2.8
通讯作者：
Helgaker, T
中科院分区：
文献类型：
--
作者：
Pecul, M;Ruud, K;Helgaker, T
我们在长度规范公式中的密度泛函理论水平上首次实现了规范原点无关的电子圆二色性（ECD），其中通过使用伦敦原子轨道确保了规范原点的独立性。我们研究了旋转强度对规范公式的选择、基组的大小以及对几种选定的小分子的密度泛函的选择的依赖性。还计算了一些较大分子的 ECD 参数，并将结果与可用的实验以及之前发布的理论数据进行比较。使用长度计公式代替速度计通常可以提供更好的基组收敛性。然而，为了获得可靠的 ECD 结果，仍然需要大的基组，并且通常需要双组扩散函数。 (C) 2004 年由 Elsevier B.V. 出版
We present the first implementation of gauge-origin independent electronic circular dichroism (ECD) at the density functional theory level in the length-gauge formulation, where gauge origin independence has been ensured through the use of London atomic orbitals. We investigate the dependence of the rotatory strengths on the choice of gauge formulation, the size of the basis set, and on the choice of density functional for several selected small molecules. The ECD parameters are also calculated for a few larger molecules, and the results are compared with experiment where available, as well as with previously published theoretical numbers. Using the length-gauge formulation instead of the velocity-gauge gives in general better basis set convergence. However, large basis sets are still needed in order to get reliable ECD results, and a double set of diffuse functions are in general required. (C) 2004 Published by Elsevier B.V.