Improved reaction and activation energies of [4+2] cycloadditions, [3,3] sigmatropic rearrangements and electrocyclizations with the spin-component-scaled MP2 method.
A new quantum mechanical scheme to calculate electronic correlation energies, spin-component-scaled MP2, was tested as a tool to predict reaction energies and barriers in computational organic chemistry. Three common pericyclic reactions with known unsatisfactory MP2 descriptions were reinvestigated with the modified MP2 approach, in which the parallel and anti-parallel spin components of the correlation energy are scaled separately. The SCS-MP2 calculated reaction and activation energies of nine Diels-Alder reactions, four [3,3] sigmatropic rearrangements, and ten electrocyclization reactions are compared to those of the MP2, B3 LYP, QCISD(T), and G3 methods. For each, the SCS-MP2 results are in excellent agreement with the experimental data and compare far more favorably to G3 than both MP2 and B3 LYP. Careful evaluation of the effect of the size of the atomic orbital (AO) basis set shows that the larger expansions improve the agreement with experiment for the SCS-MP2 method, while they get worse for both MP2 and B3 LYP.
Goumans
T P M
TP
Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Ehlers
Andreas W
AW
Lammertsma
Koop
K
Würthwein
Ernst-Ulrich
EU
Grimme
Stefan
S