Vibrational circular dichroism intensities: Ab initio vibronic coupling theory using the distributed origin gauge
Vibrational circular dichroism intensities: Ab initio vibronic coupling theory using the distributed origin gauge
复制标题
振动圆二色性强度：使用分布式原点规范的从头算振动耦合理论
DOI：
10.1063/1.463681
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发表时间：
1992
影响因子：
4.4
通讯作者：
A. Rauk
中科院分区：
文献类型：
--
作者：
Danya Yang;A. Rauk
在Nafie和Freedman的从头计算振动圆二色性（VCD）强度的振动耦合理论（VCT）中，实现了Stephens的分布原点（DO）规范。通过这种实现，可以直接比较用DO量规和共源（CO）量规获得的结果。在VCT实现中，即使在Hartree-Fock极限下，VCT - do和VCT - co的结果也是不同的。讨论了使用较小基集时VCT-DO和VCT-CO计算VCD强度的不等价性的来源和精度。对13种手性分子进行了详细的比较。八种手性氧环烷和硫环烷的实验数据可用。包括“常规”和“极化”品种的一系列基组用于NHDT、H2O2、D2O2、DOOH和恶氮吡啶。结果与Stephens磁场摄动理论的结果进行了比较。计算的VCD强度是基集和…
The distributed origin (DO) gauge of Stephens has been implemented in the ab initio vibronic coupling theory (VCT) of Nafie and Freedman for the calculation of vibrational circular dichroism (VCD) intensities. With this implementation, direct comparison is possible between results obtained with the DO gauge and the common origin (CO) gauge. In the VCT implementation, the VCT–DO and VCT–CO results are different even in the Hartree–Fock limit. The origin of the nonequivalence and the accuracy of VCD intensities by VCT–DO and VCT–CO when smaller basis sets are used are discussed. Detailed comparison is carried out for 13 chiral molecules. Experimental data are available for eight chiral oxiranes and thiiranes. A range of basis sets, of both the ‘‘conventional’’ and ‘‘polarized’’ varieties, is used for NHDT, H2O2, D2O2, DOOH, and oxaziridine. The results are compared with the results of Stephens’s magnetic‐field perturbation theory wherever the data are available. Calculated VCD intensities are basis‐set and ...