Correlation Function Formalism for Triplet Excited State Decay: Combined Spin-Orbit and Nonadiabatic Couplings

doi:10.1021/ct300798t

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	Correlation Function Formalism for Triplet Excited State Decay: Combined Spin-Orbit and Nonadiabatic Couplings
	Peng, Qian 1; Niu, Yingli 1; Shi, Qinghua 1; Gao, Xing 2; Shuai, Zhigang 2
刊名	JOURNAL OF CHEMICAL THEORY AND COMPUTATION
	2013-02-01
卷号	9 期号:2 页码:1132-1143
ISSN号	1549-9618
DOI	10.1021/ct300798t
英文摘要	Based on the second-order perturbation combining spin-orbit and nonadiabatic couplings, we derived an analytical formula for nonradiative decay rate between the triplet and singlet states by using the thermal vibration correlation function (TVCF) approach. Origin displacement, distortion, and Duschinsky rotation of the potential energy surfaces are taken into accounts within the multiple harmonic oscillator model. When coupled with first-principles calculation for the anthracene, the theoretical phosphorescence spectrum is in good agreement with the experiment. Furthermore, we found that the intersystem crossing from the first excited singlet state (S-1) to the triplet states S-1(Bu) -> T-2(Ag) is forbidden by direct spin-orbit coupling at the first-order perturbation but becomes allowed through combined spin-orbit and the nonadiabatic couplings at the second-order perturbation, and the rate is calculated to be 0.26 x 10(8) s(-1), in good agreement with the experiment. Such formalism is also applied to describe the phosphorescence quantum efficiency and the temperature dependent optical emission spectrum for factris(2-phenylpyridine) iridium. We predict that the radiative decay rate is 6.36 x 10(5) s(-1) the nonradiative decay rate is 5.04 X 10(4) s(-1) and the phosphorescence quantum efficiency is found to be 92.7% from T-1 to S-0, which reproduce well the corresponding experimental measurements.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000315018300031
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/54495]
专题	中国科学院化学研究所
通讯作者	Shuai, Zhigang
作者单位	1.Chinese Acad Sci, Inst Chem, BNLMS, Key Lab Organ Solids, Beijing 100190, Peoples R China 2.Tsinghua Univ, Dept Chem, Key Lab Organ OptoElect & Mol Engn, Beijing 100084, Peoples R China
推荐引用方式 GB/T 7714	Peng, Qian,Niu, Yingli,Shi, Qinghua,et al. Correlation Function Formalism for Triplet Excited State Decay: Combined Spin-Orbit and Nonadiabatic Couplings[J]. JOURNAL OF CHEMICAL THEORY AND COMPUTATION,2013,9(2):1132-1143.
APA	Peng, Qian,Niu, Yingli,Shi, Qinghua,Gao, Xing,&Shuai, Zhigang.(2013).Correlation Function Formalism for Triplet Excited State Decay: Combined Spin-Orbit and Nonadiabatic Couplings.JOURNAL OF CHEMICAL THEORY AND COMPUTATION,9(2),1132-1143.
MLA	Peng, Qian,et al."Correlation Function Formalism for Triplet Excited State Decay: Combined Spin-Orbit and Nonadiabatic Couplings".JOURNAL OF CHEMICAL THEORY AND COMPUTATION 9.2(2013):1132-1143.