Performance of spin-component-scaled Møller-Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions.
An examination of the performance of density-fitted, spin-component-scaled, second-order Møller-Plesset theory (SCS-MP2), SCS-MP2 with parameters optimized for nucleic acids (SCSN-MP2), and their local-correlation variants, SCS-LMP2 and SCSN-LMP2, is presented for the sandwich and T-shaped benzene dimers, the methane-benzene and H(2)S-benzene complexes, and the methane dimer over entire potential energy curves. These are compared to benchmark-quality estimates of the complete-basis-set limit for coupled-cluster theory through perturbative triple excitations, CCSD(T)/CBS. With the exception of the methane dimer, SCSN-LMP2/CBS tends to outperform SCS-LMP2/CBS with maximum relative errors of 6 and 18%, respectively, at the optimal CCSD(T)/CBS intermolecular distances. For the methane dimer, errors for SCS(N)-(L)MP2/CBS remain in the 0.2-0.3 kcal mol(-1) range, corresponding to a larger relative error of 40-50%. Although the local MP2 methods perform very similarly to their conventional counterparts when aug-cc-pVTZ or larger basis sets are used, in the absence of counterpoise correction the local approximation becomes significantly worse for the aug-cc-pVDZ basis set. The changes due to local correlation approximations for the aug-cc-pVDZ basis are reduced when diffuse functions are neglected for hydrogen atoms.
Takatani
Tait
T
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400, USA.
David Sherrill
C
C