Intruder state avoidance multireference Møller–Plesset perturbation theory

✍ Scribed by Henryk A. Witek; Yoong-Kee Choe; James P. Finley; Kimihiko Hirao

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 134 KB
• Volume: 23
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.10098

✦ Synopsis

Abstract

A new perturbation approach is proposed that enhances the low‐order, perturbative convergence by modifying the zeroth‐order Hamiltonian in a manner that enlarges any small‐energy denominators that may otherwise appear in the perturbative expansion. This intruder state avoidance (ISA) method can be used in conjunction with any perturbative approach, but is most applicable to cases where small energy denominators arise from orthogonal‐space states—so‐called intruder states—that should, under normal circumstances, make a negligible contribution to the target state of interests. This ISA method is used with multireference Møller–Plesset (MRMP) perturbation theory on potential energy curves that are otherwise plagued by singularities when treated with (conventional) MRMP; calculation are performed on the 1^3^Σ state of O~2~; and the 2^1^Δ, 3^1^Δ, 2^3^Δ, and 3^3^Δ states of AgH. This approach is also applied to other calculations where MRMP is influenced by intruder states; calculations are performed on the ^3^Π~u~ state of N~2~, the ^3^Π state of CO, and the 2^1^A′ state of formamide. A number of calculations are also performed to illustrate that this approach has little or no effect on MRMP when intruder states are not present in perturbative calculations; vertical excitation energies are computed for the low‐lying states of N~2~, C~2~, CO, formamide, and benzene; the adiabatic ^1^A~1~–^3^B~1~ energy separation in CH~2~, and the spectroscopic parameters of O~2~ are also calculated. Vertical excitation energies are also performed on the Q and B bands states of free‐base, chlorin, and zinc–chlorin porphyrin, where somewhat larger couplings exists, and—as anticipated—a larger deviation is found between MRMP and ISA‐MRMP. © 2002 Wiley Periodicals, Inc. J Comput Chem 10: 957–965, 2002