对单电子激发和双电子激发态的离子化态的运动方程耦合簇波函数进行微扰三聚物修正：理论、实现和实例。

Perturbative triples correction for the equation-of-motion coupled-cluster wave functions with single and double substitutions for ionized states: Theory, implementation, and examples.

机构信息

Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.

出版信息

J Chem Phys. 2009 Sep 21;131(11):114112. doi: 10.1063/1.3231133.

PMID:19778105

Abstract

A noniterative N(6) triples energy correction is presented for the equation-of-motion coupled-cluster method with single and double substitutions for ionized states (EOM-IP-CCSD). The correction, which is size intensive, is derived using a second-order Rayleigh-Schrodinger perturbative treatment and is similar to the approach of Stanton and Gauss [Theor. Chim. Acta 93, 303 (1996)]. In the present implementation, only the target EOM-IP states are corrected, and the reference state is described by CCSD; the method is therefore more useful for the study of the target states themselves than ionization potentials. The performance of the correction, which demonstrates the caveat above, is demonstrated by applications to singlet methylene, BNB(-), nitrogen, carbon monoxide, acetylene, benzene, thymine, and adenine.

摘要

提出了一种非迭代的 N(6)三重态能量校正方法，用于单电子和双电子激发态的运动方程耦合簇方法(EOM-IP-CCSD)。该校正方法是大小密集型的，是使用二阶瑞利-薛定谔微扰处理推导出来的，类似于 Stanton 和 Gauss [Theor. Chim. Acta 93, 303 (1996)]的方法。在目前的实现中，只校正目标 EOM-IP 态，参考态由 CCSD 描述；因此，该方法对于目标态本身的研究比电离势更有用。通过对 singlet methylene、BNB(-)、nitrogen、carbon monoxide、acetylene、benzene、thymine 和 adenine 的应用，证明了该校正方法的性能，证明了上述注意事项。