title: Performance of conventional and range-separated hybrid density functionals in calculations of electronic circular dichroism spectra of transition metal complexes.
abstract: A number of density functionals, including 'pure' (nonhybrid) functionals, global hybrids, and range-separated hybrids, were used to calculate the electronic circular dichroism (CD) spectra of 10 tris-bidentate transition metal complexes. The results are compared to one another and to experimental CD spectra, in an effort to illustrate the shortcomings of particular approximations in time-dependent density functional theory (TDDFT). The use of an origin invariant formalism to calculate magnetic transition dipole moments with the help of gauge-including atomic orbitals (GIAOs) is also investigated. With valence basis sets of moderate flexibility, good agreement between GIAO results and rotatory strengths calculated from the dipole-velocity representation is obtained for selected test cases. Empirically broadened vertical CD spectra calculated with the global hybrid functionals B3LYP and PBE0 are found to agree overall the best with experimental CD spectra.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, USA.
authors.forename: Mark
authors.initials: M
authors.lastname: Rudolph
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
mesh_terms: D002942:Circular Dichroism; D004583:Electrons; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D028561:Transition Elements