Using the ONIOM hybrid method to apply equation of motion CCSD to larger systems: Benchmarking and comparison with time-dependent density functional theory, configuration interaction singles, and time-dependent Hartree–Fock

Abstract

Equation of motion coupled-cluster singles and doubles (EOM-CCSD) is one of the most accurate computational methods for the description of one-electron vertical transitions. However, its O(N(6)) scaling, where N is the number of basis functions, often makes the study of molecules larger than 10-15 heavy atoms prohibitive. In this work we investigate how accurately less expensive methods can approximate the EOM-CCSD results. We focus on our own N-layer integrated molecular orbital molecular mechanics (ONIOM) hybrid scheme, where the system is partitioned into regions which are treated with different levels of theory. For our set of benchmark calculations, the comparison of conventional configuration interaction singles (CIS), time-dependent Hartree-Fock (TDHF), and time-dependent density functional theory (TDDFT) methods and ONIOM (with different low level methods) showed that the best accuracy-computational time combination is obtained with ONIOM(EOM:TDDFT), which has a rms of the error with respect to the conventional EOM-CCSD of 0.06 eV, compared with 0.47 eV of the conventional TDDFT.