Propagator corrections to adiabatic time-dependent density-functional theory linear response theory
Propagator corrections to adiabatic time-dependent density-functional theory linear response theory
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DOI：
10.1063/1.1836757
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发表时间：
2005-02-01
影响因子：
4.4
通讯作者：
Casida, ME
中科院分区：
文献类型：
--
作者：
Casida, ME
绝热含时密度泛函理论(TDDFT)中只有一个电子的激发是已知的。这一点在Casida对TDDFT线性响应理论的表述中尤其明显[M.E.Casida，在D.P.Chong主编的最近密度泛函方法的进展，第一部分(World Science，新加坡，1995)，第155页]。然而，为了充分描述某些激发态，特别是丁二烯的第一激发单重态和具有双基态的分子的四重激发态，显式包含两个和更高电子激发态是必要的。本文用运动方程超级算符方法导出了一个类Casida的传播子方程，它可以清楚地分为绝热部分和非绝热部分。绝热部分与绝热TDDFT线性响应理论的Casida方程相对应。这一等价性是通过推导一个一般公式来证实的，该公式包括Gonze和Scheffler导出的结果，以表明TDDFT和Gorling-Levy绝热连接微扰理论对于仅交换优化的有效势是等价的[X.Gonze和M.Scheffler，Phys.莱特牧师。82、4416(1999)]。非绝热部分显式修正了双电子和更高电子激发的绝热TDDFT。Maitra，Zhang，Cave和Burke的“Dressing TDDFT”是基态为闭壳的特例[N.T.Maitra，F.Zhang，R.J.Cave，and K.Burke，J.Chem]。太棒了。120,5932(2004)]。将Dressing TDDFT推广到基态为开壳双重态的情况，强调了在该理论中正确考虑对称性的重要性。推广到其他基态的自旋对称性是本工作的直接结果。(C)2005年美国物理研究所。
It has long been known that only one-electron excitations are available from adiabatic time-dependent density functional theory (TDDFT). This is particularly clear in Casida's formulation of TDDFT linear response theory [M. E. Casida, in Recent Advances in Density Functional Methods, Part I, edited by D. P. Chong (World Scientific, Singapore, 1995), p. 155]. Nevertheless the explicit inclusion of two- and higher-electron excitations is necessary for an adequate description of some excited states, notably the first excited singlet states of butadiene and quartet excited states of molecules with a doublet ground state. The equation-of-motion superoperator approach is used here to derive a Casida-like propagator equation which can be clearly separated into an adiabatic part and a nonadiabatic part. The adiabatic part is identified as corresponding to Casida's equation for adiabatic TDDFT linear response theory. This equivalence is confirmed by deriving a general formula which includes the result that Gonze and Scheffler derived to show the equivalence of TDDFT and Gorling-Levy adiabatic connection perturbation theory for the exchange-only optimized effective potential [X. Gonze and M. Scheffler, Phys. Rev. Lett. 82, 4416 (1999)]. The nonadiabatic part explicitly corrects adiabatic TDDFT for two- and higher-electron excitations. The "dressed TDDFT" of Maitra, Zhang, Cave, and Burke is obtained as a special case where the ground state is closed shell [N. T. Maitra, F. Zhang, R. J. Cave, and K. Burke, J. Chem. Phys. 120, 5932 (2004)]. The extension of dressed TDDFT to the case where the ground state is an open-shell doublet is presented, highlighting the importance of correctly accounting for symmetry in this theory. The extension to other ground state spin symmetries is a straightforward consequence of the present work. (C) 2005 American Institute of Physics.