期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 17, 期 29, 页码 19079-19086出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp02590g
关键词
-
资金
- Polish National Science Center [2012/05/B/ST4/01236]
- Norwegian Supercomputing Program [NN4654K]
- COST-CMTS Action COnvergent Distributed Environment for Computational Spectroscopy (CODECS)'' [CM1002]
We present a computational methodology to calculate the intensity of circular dichroism (CD) in spin-forbidden absorption and of circularly polarized phosphorescence (CPP) signals, a manifestation of the optical activity of the triplet-singlet transitions in chiral compounds. The protocol is based on the response function formalism and is implemented at the level of time-dependent density functional theory. It has been employed to calculate the spin-forbidden circular dichroism and circularly polarized phosphorescence signals of valence n -> pi* and n <- pi* transitions, respectively, in several chiral enones and diketones. Basis set effects in the length and velocity gauge formulations have been explored, and the accuracy achieved when employing approximate (mean-field and effective nuclear charge) spin-orbit operators has been investigated. CPP is shown to be a sensitive probe of the triplet excited state structure. In many cases the sign of the spin-forbidden CD and CPP signals are opposite. For the beta,gamma-enones under investigation, where there are two minima on the lowest triplet excited state potential energy surface, each minimum exhibits a CPP signal of a different sign.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据