Locally correlated equation-of-motion coupled cluster theory for the excited states of large molecules

Document Type

Article

Abstract

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.

Department(s)

Chemistry

Publication Title

Chemical Physics Letters

Volume

366

Issue

5-6

First Page

611

Last Page

622

Publication Date

12-20-2002

DOI

10.1016/S0009-2614(02)01639-1

ISSN

00092614

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