Performance of TD-DFT for Excited States of Open-Shell Transition Metal   Compounds

doi:10.1021/acs.jpca.7b00752

CORC > 北京大学 > 化学与分子工程学院

	Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds
	Suo, Bingbing ; Shen, Kaiyuan ; Li, Zhendong ; Liu, Wenjian
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2017
关键词	DENSITY-FUNCTIONAL THEORY MULTIREFERENCE PERTURBATION-THEORY GAUSSIAN-BASIS SETS GENERALIZED-GRADIENT-APPROXIMATION CORRELATED MOLECULAR CALCULATIONS CONFIGURATION-INTERACTION METHOD POTENTIAL-ENERGY SURFACES MODEL-SPACE COEFFICIENTS COUPLED-CLUSTER METHOD ANO BASIS-SETS
DOI	10.1021/acs.jpca.7b00752
英文摘要	Time-dependent density functional theory (TD-DFT) has been very successful in accessing low-lying excited states of closed-shell systems. However, it is much less so for excited states of open-shell systems: unrestricted Kohn-Sham based TD-DFT (U-TD-DFT) often produces physically meaningless excited states due to heavy spin contaminations, whereas restricted Kohn-Sham based TD-DFT often misses those states of lower energies. A much better variant is the explicitly spin-adapted TD-DFT (X-TD-DFT) [J. Chem. Phys. 2011, 135, 194106] that can capture all the spin-adapted singly excited states yet without computational overhead over U-TD-DFT. While the superiority of X-TD-DFT over U-TD-DFT has been demonstrated for open-shell systems of main group elements, it remains to be seen if this is also the case for open-shell transition metal compounds. Taking as benchmark the results by MS-CASPT2 (multistate complete active space second-order perturbation theory) and ic-MRCISD (internally contracted multireference configuration interaction with singles and doubles), it is shown that X-TD-DFT is indeed superior to U-TD-DFT for the vertical excitation energies of ZnH, CdH, ScH2, YH2, YO, and NbO2. Admittedly, there exist a few cases where U-TD-DFT appears to be better than X-TD-DFT. However, this is due to a wrong reason: the underestimation (due to spin contamination) and the overestimation (due to either the exchange-correlation functional itself or the adiabatic approximation to the exchange-correlation kernel) happen to be compensated in the case of U-TD-DFT. As for [Cu(C6H6)(2)](2+), which goes beyond the capability of both MS-CASPT2 and ic-MRCISD, X-TD-DFT revises the U-TD-DFT assignment of the experimental spectrum.; National Natural Science Foundation of China [21603134, 21673174, 21273011, 21290192]; Double First-class University Construction Project of Northwest University; SCI(E); ARTICLE; 20; 3929-3942; 121
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/473328]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Suo, Bingbing,Shen, Kaiyuan,Li, Zhendong,et al. Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2017.
APA	Suo, Bingbing,Shen, Kaiyuan,Li, Zhendong,&Liu, Wenjian.(2017).Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds.JOURNAL OF PHYSICAL CHEMISTRY A.
MLA	Suo, Bingbing,et al."Performance of TD-DFT for Excited States of Open-Shell Transition Metal Compounds".JOURNAL OF PHYSICAL CHEMISTRY A (2017).