Locally correlated equation-of-motion coupled cluster theory for the excited states of large molecules
We report an extension of the local correlation concept to electronically excited states via the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method. We apply the same orbital domain structure used successfully for ground-state CCSD by Werner and co-workers and find that the resulting localized excitation energies are in error generally by less than 0.2 eV relative to their canonical EOM-CCSD counterparts, provided the basis set is flexible and includes Rydberg-like functions. In addition, we account for weak-pair contributions efficiently using a correction to local-EOM-CCSD transition energies based on the perturbative (D) correction used with configuration interaction singles (CIS). © 2002 Elsevier Science B.V. All rights reserved.
Chemical Physics Letters
Daniel Crawford, T. and King, Rollin A., "Locally correlated equation-of-motion coupled cluster theory for the excited states of large molecules" (2002). Chemistry Faculty Publications. 21.