Combining the spin-separated exact two-component relativistic   Hamiltonian with the equation-of-motion coupled-cluster method for the   treatment of spin-orbit splittings of light and heavy elements

doi:10.1039/c6cp07588f

CORC > 北京大学 > 化学与分子工程学院

	Combining the spin-separated exact two-component relativistic Hamiltonian with the equation-of-motion coupled-cluster method for the treatment of spin-orbit splittings of light and heavy elements
	Cao, Zhanli ; Li, Zhendong ; Wang, Fan ; Liu, Wenjian
刊名	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
	2017
关键词	MOLECULAR QUANTUM-MECHANICS ANO BASIS-SETS CONFIGURATION-INTERACTION WAVE-FUNCTIONS FOCK-SPACE PROGRAM PACKAGE SHELL SYSTEMS DENSITY STATES CHEMISTRY
DOI	10.1039/c6cp07588f
英文摘要	The spin-separated exact two-component (X2C) relativistic Hamiltonian [sf-X2C+ so-DKHn, J. Chem. Phys., 2012, 137, 154114] is combined with the equation-of-motion coupled-cluster method with singles and doubles (EOM-CCSD) for the treatment of spin-orbit splittings of open-shell molecular systems. Scalar relativistic effects are treated to infinite order from the outset via the spin-free part of the X2C Hamiltonian (sf-X2C), whereas the spin-orbit couplings (SOC) are handled at the CC level via the first-order Douglas-Kroll-Hess (DKH) type of spin-orbit operator (so-DKH1). Since the exponential of single excitations, i.e., exp(T-1), introduces sufficient spin orbital relaxations, the inclusion of SOC at the CC level is essentially the same in accuracy as the inclusion of SOC from the outset in terms of the two-component spinors determined variationally by the sf-X2C+ so-DKH1 Hamiltonian, but is computationally more efficient. Therefore, such an approach (denoted as sf-X2C-EOM-CCSD(SOC)) can achieve uniform accuracy for the spin-orbit splittings of both light and heavy elements. For light elements, the treatment of SOC can even be postponed until the EOM step (denoted as sf-X2C-EOM(SOC)-CCSD), so as to further reduce the computational cost. To reveal the efficacy of sf-X2C-EOM-CCSD(SOC) and sf-X2C-EOM(SOC)-CCSD, the spin-orbit splittings of the (2)Pi states of monohydrides up to the sixth row of the periodic table are investigated. The results show that sf-X2C-EOM-CCSD(SOC) predicts very accurate results (within 5%) for elements up to the fifth row, whereas sf-X2C-EOM(SOC)-CCSD is useful only for light elements (up to the third row but with some exceptions). For comparison, the sf-X2C-S-TD-DFT-SOC approach [spin-adapted open-shell time-dependent density functional theory, Mol. Phys., 2013, 111, 3741] is applied to the same systems. The overall accuracy (1-10%) is satisfactory.; NSFC [21473116, 21273155, 21273011, 21290192]; SCI(E); ARTICLE; 5; 3713-3721; 19
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/475199]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Cao, Zhanli,Li, Zhendong,Wang, Fan,et al. Combining the spin-separated exact two-component relativistic Hamiltonian with the equation-of-motion coupled-cluster method for the treatment of spin-orbit splittings of light and heavy elements[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2017.
APA	Cao, Zhanli,Li, Zhendong,Wang, Fan,&Liu, Wenjian.(2017).Combining the spin-separated exact two-component relativistic Hamiltonian with the equation-of-motion coupled-cluster method for the treatment of spin-orbit splittings of light and heavy elements.PHYSICAL CHEMISTRY CHEMICAL PHYSICS.
MLA	Cao, Zhanli,et al."Combining the spin-separated exact two-component relativistic Hamiltonian with the equation-of-motion coupled-cluster method for the treatment of spin-orbit splittings of light and heavy elements".PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2017).