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

Abstract

To cite this article: P. Papp , P. Neogrady , P. Mach , J. Pittner , I. Huba[cbreve] & S. Wilson (2008) Many-body Brillouin-Wigner second-order perturbation theory: an application to the autoaromatisation of hex-3-ene-1,5-diyne (the 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. Møller-Plesset (MP2) theory, and in the multireference case can be shown to be equivalent to state-specfic multireference Rayleigh-Schro¨dinger-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.

The bergman cyclizations of the enediyne and its N‐substituted analogs using multiconfigurational second‐order perturbation theory

“…The Bergman cyclization of 1R (reaction 1 in Scheme 1) may be induced both thermally and photochemically. [9,10] The thermal Bergman cyclization of 1R has been extensively studied both experimentally and theoretically. [7,[11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] McMahon et al [21] determined the structure of 1R using Fourier transform microwave spectroscopy and the key parameter (the C 1 AC 6 distance, see Scheme 1) governing reactivity of the Bergman cyclization reaction was reported to be 4.321 Å .…”

Analytic gradient for the multireference Brillouin-Wigner coupled cluster method and for the state-universal multireference coupled cluster method

“…The latter group is then divided into state universal and state-specific subgroups. [45][46][47] However, the price paid is the lack of size extensivity of the method, which is dealt with by various size-extensivity corrections. On the other hand, in the case of state-specific methods ͑see, e.g., Refs.…”

Many‐body Brillouin–Wigner second‐order perturbation theory: A robust and efficient approach to the multireference correlation problem

“…Given the success of “ MP2 ”/“ MBPT2 ” theory for problems for which a single reference function is appropriate, it is important to determine the extent to which the corresponding Brillouin–Wigner method is applicable in a state‐specific formulation with a posteriori modification to problems, which demand the use of a multireference approach. In two recent articles 30, 31, comparisons of (single reference) “ MP2 ”/“ MBPT2 ” and (multireference) second‐order modified Brillouin–Wigner calculations have been reported. In the first of these articles 30, the dissociation of the first‐row diatomic hydride molecules BH and FH is investigated using basis sets for which the corresponding full configuration interaction calculations can be carried out.…”

“…In the first of these articles 30, the dissociation of the first‐row diatomic hydride molecules BH and FH is investigated using basis sets for which the corresponding full configuration interaction calculations can be carried out. In the second article 31, second‐order multireference many‐body Brillouin–Wigner perturbation theory is used to study the Bergman reaction; that is, the autoaromatization of hex‐3‐ene‐1,5‐diyne.…”