Eliminating the domain error in local explicitly correlated second-order Møller-Plesset perturbation theory.
A new explicitly correlated local MP2-F12 method is proposed in which the error caused by truncating the virtual orbital space to pair-specific local domains is almost entirely removed. This is achieved by a simple modification of the ansatz for the explicitly correlated wave function, which makes it possible that the explicitly correlated terms correct both for the basis set incompleteness error as well as for the domain error in the LMP2. Benchmark calculations are presented for 21 molecules and 16 chemical reactions. The results demonstrate that the local approximations have hardly any effect on the accuracy of the computed correlation energies and reaction energies, and the LMP2-F12 reaction energies agree within 0.1-0.2 kcal/mol with estimated MP2 basis set limits.
Werner
Hans-Joachim
HJ
Institut fur Theoretische Chemie, Universitat Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. werner@theochem.uni-stuttgart.de