title: Oscillator Strength: How Does TDDFT Compare to EOM-CCSD?
abstract: In this work, we compare a large variety of density functionals against the equation of motion coupled cluster singles and doubles (EOM-CCSD) method for the calculation of oscillator strengths. Valence and Rydberg states are considered for a test set composed of 11 small organic molecules. In our previous work, the same systems and methods were tested against experimental results for the excitation energies. The results from this investigation confirm our previous findings, i.e., that there is a large difference between the functionals. For the oscillator strength, the average best agreement with EOM-CCSD is provided by CAM-B3LYP followed by LC-ωPBE and, to a lesser extent, B3P86 and LC-BLYP.
authors.affiliation: Gaussian, Inc., 340 Quinnipiac St., Bldg. 40, Wallingford, Connecticut 06492, United States, and Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, United States.
authors.forename: Marco
authors.initials: M
authors.lastname: Caricato
authors.affiliation: Gaussian, Inc., 340 Quinnipiac St., Bldg. 40, Wallingford, Connecticut 06492, United States, and Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, United States.
authors.forename: Gary W
authors.initials: GW
authors.lastname: Trucks
authors.affiliation: Gaussian, Inc., 340 Quinnipiac St., Bldg. 40, Wallingford, Connecticut 06492, United States, and Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Frisch
authors.affiliation: Gaussian, Inc., 340 Quinnipiac St., Bldg. 40, Wallingford, Connecticut 06492, United States, and Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, United States.
authors.forename: Kenneth B
authors.initials: KB
authors.lastname: Wiberg