Dual-basis second-order Moller-Plesset perturbation theory: A reduced-cost reference for correlation calculations.
The resolution-of-the-identity (RI) approximation has placed the onus of the cost of a second-order Moller-Plesset (MP2) calculation on the underlying self-consistent field (SCF) calculation for many moderately sized molecules. A dual-basis approach to the SCF calculation, based on previous methods demonstrated for density functional theory, is combined with RI-MP2 calculations, and small basis subsets for cc-pVTZ, cc-pVQZ, and 6-311++G(3df,3pd) are presented. These subsets provide time savings of greater than 90%, with negligible errors in absolute and relative energies, compared to the associated full-basis counterpart. The method is tested with a series of rotational barriers, relative conformational energies of alanine tetrapeptides, as well as the full G3/99 molecular set. RI-MP2 calculations on alanine octapeptides (40 heavy atoms, 3460 basis functions), using cc-pVQZ, are presented. Results improve upon previous methods that diagonalize the virtual space separately.
Steele
Ryan P
RP
Department of Chemistry, University of California, Berkeley, California 94720, USA. ofer4@bastille.cchem.berkeley.edu
DiStasio
Robert A
RA
Shao
Yihan
Y
Kong
Jing
J
Head-Gordon
Martin
M