Time-dependent quasirelativistic density-functional theory based on the   zeroth-order regular approximation

doi:10.1063/1.2047554

CORC > 北京大学 > 化学与分子工程学院

	Time-dependent quasirelativistic density-functional theory based on the zeroth-order regular approximation
	Peng, DL ; Zou, WL ; Liu, WJ
刊名	journal of chemical physics
	2005
关键词	SPECTROSCOPIC CONSTANTS EXCITATION-ENERGIES PROGRAM PACKAGE EXCITED-STATES WAVE-FUNCTIONS ELECTRON 4-COMPONENT EQUATIONS SYSTEMS ATOMS
DOI	10.1063/1.2047554
英文摘要	A time-dependent quasirelativistic density-functional theory for excitation energies of systems containing heavy elements is developed, which is based on the zeroth-order regular approximation (ZORA) for the relativistic Hamiltonian and a noncollinear form for the adiabatic exchange-correlation kernel. To avoid the gauge dependence of the ZORA Hamiltonian a model atomic potential, instead of the full molecular potential, is used to construct the ZORA kinetic operator in ground-state calculations. As such, the ZORA kinetic operator no longer responds to changes in the density in response calculations. In addition, it is shown that, for closed-shell ground states, time-reversal symmetry can be employed to simplify the eigenvalue equation into an approximate form that is similar to that of time-dependent nonrelativistic density-functional theory. This is achieved by invoking an independent-particle approximation for the induced density matrix. The resulting theory is applied to investigate the global potential-energy curves of low-lying Lambda S- and omega omega-coupled electronic states of the AuH molecule. The derived spectroscopic parameters, including the adiabatic and vertical excitation energies, equilibrium bond lengths, harmonic and anharmonic vibrational constants, fundamental frequencies, and dissociation energies, are in good agreement with those of time-dependent four-component relativistic density-functional theory and ab initio multireference second-order perturbation theory. Nonetheless, this two-component relativistic version of time-dependent density-functional theory is only moderately advantageous over the four-component one as far as computational efforts are concerned. (c) 2005 American Institute of Physics.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000232532000004&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Physics, Atomic, Molecular & Chemical; SCI(E); EI; PubMed; 39; ARTICLE; 14; 144101; 123
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/199058]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Peng, DL,Zou, WL,Liu, WJ. Time-dependent quasirelativistic density-functional theory based on the zeroth-order regular approximation[J]. journal of chemical physics,2005.
APA	Peng, DL,Zou, WL,&Liu, WJ.(2005).Time-dependent quasirelativistic density-functional theory based on the zeroth-order regular approximation.journal of chemical physics.
MLA	Peng, DL,et al."Time-dependent quasirelativistic density-functional theory based on the zeroth-order regular approximation".journal of chemical physics (2005).