Approximate equation-of-motion coupled-cluster methods for electron affinities of closed-shell molecules.

Abstract

We investigate performance of the equation-of-motion coupled-cluster method at the single and doubles level (EOM-CCSD) and a series of approximate methods based on EOM-CCSD on electron affinities (EA) of closed-shell cations and neutral molecules with positive and negative EAs in this work. Our results confirm that P-EOM-MBPT2 can provide reasonable EAs when molecules with significant multireference character are not considered and its mean absolute error on EAs of these molecules is around or less than 0.2 eV. Its accuracy is comparable to that of the more expensive EOM-CCSD(2) method. Results of EOM-CCSD(2), P-EOM-MBPT2, and CIS(D∞) indicate that the [[H, ac +], T2] term in the 1h2p-1h block is more important on EAs than the term neglected in the 1h2p-1h2p block in P-EOM-MBPT2. We proposed an economical method where EAs from CIS(D∞) are corrected by treating this [[H, ac +], T2] term in the 1h2p-1h block perturbatively [corr-CIS(D∞)]. EAs with corr-CIS(D∞) agree very well with those of P-EOM-MBPT2 with a difference of less than 0.02 eV. Computational scaling of this method is N4 for the iterative part and N5 for some non-iterative steps. Its storage requirement is only of OV3. Corr-CIS(D∞) is an economical and reliable method on EAs, and it can be applied to EAs of large molecules.