Time-dependent four-component relativistic density-functional theory for excitation energies. II. The exchange-correlation kernel.
Time-dependent four-component relativistic density-functional theory for excitation energies. II. The exchange-correlation kernel.
复制标题
DOI：
10.1063/1.1940609
复制
发表时间：
2005-08
期刊：
影响因子：
--
通讯作者：
Jun Gao;Wenli Zou;Wenjian Liu;Yunlong Xiao;Daoling Peng;Bo Song;Chengbu Liu
中科院分区：
文献类型：
--
作者：
Jun Gao;Wenli Zou;Wenjian Liu;Yunlong Xiao;Daoling Peng;Bo Song;Chengbu Liu
我们推广了我们以前的含时四分量相对论密度泛函理论[J.Gao，W.Liu，B.Song，和C.Liu，J.Chem.太棒了。121,6658(2004)]通过使用交换相关核的非共线形式。这种新的形式可以处理包含矩(自旋)翻转组态的激发态，否则用普通的交换关联泛函是不能得到的。作为第一个应用，研究了AuH分子16个低位omega-omega耦合电子态的全局势能曲线。得到的光谱参数，包括绝热和垂直激发能、平衡键长、简谐和非谐振动常数、基频和离解能，与从头算多参考二阶微扰理论和已有的实验数据基本一致。
We extend our previous formulation of time-dependent four-component relativistic density-functional theory [J. Gao, W. Liu, B. Song, and C. Liu, J. Chem. Phys. 121, 6658 (2004)] by using a noncollinear form for the exchange-correlation kernel. The new formalism can deal with excited states involving moment (spin)-flipped configurations which are otherwise not accessible with ordinary exchange-correlation functionals. As a first application, the global potential-energy curves of 16 low-lying omega omega-coupled electronic states of the AuH molecule have been investigated. 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 grossly in good agreement with those of ab initio multireference second-order perturbation theory and the available experimental data.