title: Spin-orbit treatment of UV-vis absorption spectra and photophysics of rhenium(I) carbonyl-bipyridine complexes: MS-CASPT2 and TD-DFT analysis.
abstract: The lowest-lying spectral transitions in [ReX(CO)(3)(bpy)] (X = Cl, Br, I; bpy = 2,2'-bipyridine) complexes were calculated by means of spin-orbit time-dependent density functional theory (SO-TD-DFT) and spin-orbit multistate complete active space second-order perturbation theory (SO-MS-CASPT2). Computational results are compared with absorption spectra measured in different solvents and used to qualitatively explain the temperature dependence of the phosphorescence decay parameters that were measured for the whole series of complexes. Spin-orbit excited-state calculations interpret their electronic absorption spectra as arising from a bunch of spin mixed states with a singlet component of only 50-90% (depending on the halide), and attribute the phosphorescence decay to thermal population of spin-mixed states with a substantial singlet character.
authors: J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-182 23 Prague, Czech Republic.
authors: Radka
authors: R
authors: Heydová
authors: Etienne
authors: E
authors: Gindensperger
authors: Roberta
authors: R
authors: Romano
authors: Jan
authors: J
authors: Sýkora
authors: Antonín
authors: A
authors: Vlček
authors: Stanislav
authors: S
authors: Záliš
authors: Chantal
authors: C
authors: Daniel
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives / Q000737:chemistry*; D002248:Carbon Monoxide / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D011789:Quantum Theory; D012211:Rhenium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D009942:Organometallic Compounds; D015082:2,2'-Dipyridyl; D012211:Rhenium; D002248:Carbon Monoxide