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

Peter Papp (1) , Pavel Neogrady (1) , Pavel Mach (1) , Jiri Pittner (2) , Ivan Hubac (1) , Stephen Wilson (1, 3)

1 Comenius University in Bratislava
2 J. Heyrovsky Institute of Physical Chemistry
3 Physical and Theoretical Chemistry Laboratory

The multireference, state specific, second order, Brillouin-Wigner perturbation theory is applied to the autoaromatization 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. Moller-Plesset (MP2) theory, and in the multireference case can be shown to be equivalent to state specfic multireference Rayleigh-Schrodinger 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.

Mots clés: Physical Sciences

Peter Papp, Pavel Neogrady, Pavel Mach, Jiri Pittner, Ivan Hubac, et al.. Many-body Brillouin-Wigner second order perturbation theory: An application to the autoaromatization of hex-3-ene-1,5-diyne (the Bergman reaction). Molecular Physics, 2008, 106 (01), pp.57-74. ⟨10.1080/00268970701832355⟩. ⟨hal-00513169⟩