Efficient Implementation of Equation-of-Motion Coupled-Cluster Singles and Doubles Method with the Density-Fitting Approximation: An Enhanced Algorithm for the Particle–Particle Ladder Term

Abstract

An efficient implementation of the density-fitted equation-of-motion coupled-cluster singles and doubles (DF-EOM-CCSD) method is presented with an enhanced algorithm for the particle–particle ladder (PPL) term, which is the most expensive part of EOM-CCSD computations. To further improve the evaluation of the PPL term, a hybrid density-fitting/Cholesky decomposition (DF/CD) algorithm is also introduced. In the hybrid DF/CD approach, four virtual index integrals are constructed on-the-fly from the DF factors; then, their partial Cholesky decomposition is simultaneously performed. The computational cost of the DF-EOM-CCSD method for excitation energies is compared with that of the resolution of the identity EOM-CCSD (RI-EOM-CCSD) (from the Q-chem 5.3 package). Our results demonstrate that DF-EOM-CCSD excitation energies are significantly accelerated compared to RI-EOM-CCSD. There is more than a 2-fold reduction for the C8H18 molecule in the cc-pVTZ basis set with the restricted Hartree-Fock (RHF) reference. This cost savings results from the efficient evaluation of the PPL term. In the RHF based DF-EOM-CCSD method, the number of flops (NOF) is 1/4O2V4, while that of RI-EOM-CCSD was reported (Epifanovsky et al. J. Chem. Phys.2013, 139, 13410524116550) to be 5/8O2V4 for the PPL contraction term. Further, the NOF of VVVV-type integral transformation is 1/2V4Naux in our case, while it appears to be V4Naux for RI-EOM-CCSD. Hence, our implementation is 2.5 and 2.0 times more efficient compared to RI-EOM-CCSD for these expensive terms. For the unrestricted Hartree-Fock (UHF) reference, our implementation maintains its enhanced performance and provides a 1.8-fold reduction in the computational time compared to RI-EOM-CCSD for the C7H16 molecule. Our results indicate that our DF-EOM-CCSD implementation is 1.7 and 1.4 times more efficient compared with RI-EOM-CCSD for average computational cost per EOM-CCSD iteration. Moreover, our results show that the new hybrid DF/CD approach improves upon the DF algorithm, especially for large molecular systems. Overall, we conclude that the new hybrid DF/CD PPL algorithm is very promising for large-sized chemical systems.