Analytic energy gradients for the coupled-cluster singles and doubles with perturbative triples method with the density-fitting approximation.

Abstract

An efficient implementation of analytic gradients for the coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method with the density-fitting (DF) approximation, denoted as DF-CCSD(T), is reported. For the molecules considered, the DF approach substantially accelerates conventional CCSD(T) analytic gradients due to the reduced input/output time and the acceleration of the so-called "gradient terms": formation of particle density matrices (PDMs), computation of the generalized Fock-matrix (GFM), solution of the Z-vector equation, formation of the effective PDMs and GFM, back-transformation of the PDMs and GFM, from the molecular orbital to the atomic orbital (AO) basis, and computation of gradients in the AO basis. For the largest member of the molecular test set considered (C6H14), the computational times for analytic gradients (with the correlation-consistent polarized valence triple-ζ basis set in serial) are 106.2 [CCSD(T)] and 49.8 [DF-CCSD(T)] h, a speedup of more than 2-fold. In the evaluation of gradient terms, the DF approach completely avoids the use of four-index two-electron integrals. Similar to our previous studies on DF-second-order Møller-Plesset perturbation theory and DF-CCSD gradients, our formalism employs 2- and 3-index two-particle density matrices (TPDMs) instead of 4-index TPDMs. Errors introduced by the DF approximation are negligible for equilibrium geometries and harmonic vibrational frequencies.