Many-body Brillouin-Wigner second-order perturbation theory: an application to the autoaromatisation of hex-3-ene-1,5-diyne (the Bergman reaction)

被引：5

作者：

Papp, P. ^{[3
]}

Neogrady, P. ^{[2
]}

Mach, P. ^{[1
]}

Pittner, J. ^{[4
]}

Hubac, I. ^{[1
,5
]}

Wilson, S. ^{[1
,5
]}

机构：

[1] Comenius Univ, Fac Math Phys & Informat, Dept Nucl Phys & Biophy, Bratislava, Slovakia

[2] Comenius Univ, Fac Nat Sci, Dept Phys & Theoret Chem, Bratislava, Slovakia

[3] Comenius Univ, Fac Math Phys & Informat, Dept Expt Phys, Bratislava, Slovakia

[4] Silesian Univ, Inst Phys, Opava, Czech Republic

[5] Univ Oxford, Phys & Theoret Chem Lab, Oxford, England

来源：

MOLECULAR PHYSICS | 2008年 / 106卷 / 01期

关键词：

electron correlation; multireference; Brillouin-Wigner; perturbation theory; Bergman reaction;

D O I：

10.1080/00268970701832355

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The multireference, state specific, second-order, Brillouin-Wigner perturbation theory is applied to the autoaromatisation of hex-3-ene-1,5-diyne, the Bergman reaction. Calculations are reported for the reactant (hex-3-ene-1,5-diyne), the transition state and the product (1,4-didehydrobenzene). A posteriori modifications are made which, in the case of a single reference function, recover the well-known formula of second-order many-body perturbation theory, i.e. Mller-Plesset (MP2) theory, and in the multireference case can be shown to be equivalent to state-specfic multireference Rayleigh-Schrdinger-like perturbation theory. Calculations are performed for a sequence of correlation consistent basis sets and, by extrapolation, complete basis set limits of the energetics of the Bergman reaction are estimated.

引用

页码：57 / 74

页数：18