Structures and harmonic vibrational frequencies for excited states of diatomic molecules with CCSD(R12) and CCSD(F12) models

Jun Yang and Christof Hättig
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätsstrasse 150 D-44801 Bochum, Germany

J. Chem. Phys., 130, 124101 (2009).
(Received 27 November 2008; accepted 12 February 2009; published online 23 March 2009)

The equation-of-motion coupled-cluster method for excited states with the singles-and-doubles model (CCSD) has been implemented for ansatz 2 of the explicitly correlated CCSD(R12) and CCSD(F12) methods as part of the program package Dalton. In this model, an orthonormal complementary auxiliary basis set is used for the resolution-of-identity approximation in order to calculate the three-electron integrals needed for CCSD(R12) and CCSD(F12). The additional CCSD(R12) or CCSD(F12) terms introduced within ansatz 2, which are not present in ansatz 1, are derived and discussed with regard to the extra costs needed for their computation. As a first application the basis set convergence of equilibrium bond lengths and harmonic vibrational frequencies has been investigated for some singlet excited states of the diatomic molecules N2, CO, BF, and BH. The calculated CCSD(F12) results show that the average absolute deviations of the bond lengths and frequencies from the basis set limits are below 0.1 pm and 5 cm-1 as well as 0.05 pm and 1 cm-1 for the triple- and quadruple-ζ basis sets, respectively. These deviations are shown to largely arise from the SCF basis set incompleteness errors.

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