Coupled cluster methods including triple excitations for excited states of radicals

Document Type

Article

Abstract

We report an extension of the coupled cluster iterative-triples model, CC3, to excited states of open-shell molecules, including radicals. We define the method for both spin-unrestricted Hartree-Fock (UHF) and spin-restricted open-shell Hartree-Fock (ROHF) reference determinants and discuss its efficient implementation in the PSI3 program package. The program is streamlined to use at most O(N 7) computational steps and avoids storage of the triple-excitation amplitudes for both the ground- and excited-state calculations. The excitation-energy program makes use of a Löwdin projection formalism (comparable to that of earlier implementations) that allows computational reduction of the Davidson algorithm to only the single- and double-excitation space, but limits the calculation to only one excited state at a time. However, a root-following algorithm may be used to compute energies for multiple states of the same symmetry. Benchmark applications of the new methods to the lowest valence 2B 1 state of the allyl radical, low-lying states of the CH and CO + diatomics, and the nitromethyl radical show substantial improvement over ROHF- and UHF-based CCSD excitation energies for states with strong double-excitation character or cases suffering from significant spin contamination. For the allyl radical, CC3 adiabatic excitation energies differ from experiment by less than 0.02 eV, while for the 2Σ + state of CH, significant errors of more than 0.4 eV remain. © 2005 American Institute of Physics.

Department(s)

Chemistry

Publication Title

Journal of Chemical Physics

Volume

122

Issue

5

Publication Date

8-9-2005

DOI

10.1063/1.1835953

ISSN

00219606

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