Energy and analytic gradients for the orbital-optimized coupled-cluster doubles method with the density-fitting approximation: An efficient implementation

摘要

Efficient implementations of the orbital-optimized coupled-cluster doubles (or simply "optimized CCD," OCCD, for short) method and its analytic energy gradients with the density-fitting (DF) approach, denoted by DF-OCCD, are presented. In addition to the DF approach, the Cholesky-decomposed variant (CD-OCCD) is also implemented for energy computations. The computational cost of the DF-OCCD method (available in a plugin version of the DFOCC module of PSI4) is compared with that of the conventional OCCD (from the Q-CHEM package). The OCCD computations were performed with the Q-CHEM package in which OCCD are denoted by OD. In the conventional OCCD method, one needs to perform four-index integral transformations at each of the CCD iterations, which limits its applications to large chemical systems. Our results demonstrate that DF-OCCD provides dramatically lower computational costs compared to OCCD, and there are almost eightfold reductions in the computational time for the C6H14 molecule with the cc-pVTZ basis set. For open-shell geometries, interaction energies, and hydrogen transfer reactions, DF-OCCD provides significant improvements upon DF-CCD. Furthermore, the performance of the DF-OCCD method is substantially better for harmonic vibrational frequencies in the case of symmetry-breaking problems. Moreover, several factors make DF-OCCD more attractive compared to CCSD: (1) for DF-OCCD, there is no need for orbital relaxation contributions in analytic gradient computations; (2) active spaces can readily be incorporated into DF-OCCD; (3) DF-OCCD provides accurate vibrational frequencies when symmetry-breaking problems are observed; (4) in its response function, DF-OCCD avoids artificial poles; hence, excited-state molecular properties can be computed via linear response theory; and (5) symmetric and asymmetric triples corrections based on DF-OCCD [DF-OCCD(T)] have a significantly better performance in near degeneracy regions.