Quartic-scaling analytical energy gradient of scaled opposite-spin second-order Moller-Plesset perturbation theory

摘要

The analytical gradient of the '' scaled opposite spin '' (SOS-) and '' modified opposite spin '' (MOS-) second-order M circle divide ller-Plesset perturbation theory (MP2) methods is derived and implemented. Both energy and the first derivative can be evaluated efficiently with a fourth-order scaling algorithm by using a combination of auxiliary basis expansions and Laplace transformation techniques as opposed to the traditional fifth-order approach of MP2. A statistical analysis of 178 small molecules suggests that the new gradient scheme provides geometries of MP2 quality, indicating the reliability of the method in general chemical applications. A more specific study of the group VI transition metal carbonyl complexes indicates that the new scheme improves the MP2 description relative to available experimental data and higher-order theories. The proposed gradient scheme thus endeavors to obtain improved structural features at reduced computational cost.