Collect. Czech. Chem. Commun.
1988, 53, 2239-2249
https://doi.org/10.1135/cccc19882239
Effect of electron correlation on SN2 activation barriers. Fourth-order MBPT calculations
Ivan Černušák and Miroslav Urban
Department of Physical Chemistry, Comenius University, Mlynská Dolina CH-1, CS-842 15 Bratislava
Abstract
The activation barriers for a series of model gas-phase nucleophilic displacement reactions have been calculated at the MBPT(4)/DZ + P + D level. Electron correlation significantly reduces the barrier height, in most cases by about 50%. The role of individual contributions up to the fourth order MBPT is analyzed in detail showing the vital importance of single and triple excitations.
