Spin-orbit treatment of UV-vis absorption spectra and photophysics of rhenium(I) carbonyl-bipyridine complexes: MS-CASPT2 and TD-DFT analysis

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)...

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Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 116; no. 46; p. 11319
Main Authors: Heydová, Radka, Gindensperger, Etienne, Romano, Roberta, Sýkora, Jan, Vlček, Jr, Antonín, Záliš, Stanislav, Daniel, Chantal
Format: Journal Article
Language:English
Published: United States 26.11.2012
Subjects:
2,2'-Dipyridyl - analogs & derivatives
2,2'-Dipyridyl - chemistry
Carbon Monoxide - chemistry
Molecular Structure
Organometallic Compounds - chemistry
Photochemical Processes
Quantum Theory
Rhenium - chemistry
Spectrophotometry, Ultraviolet
Time Factors
ISSN:1520-5215, 1520-5215
Online Access:Get more information
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Summary: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.
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ISSN:1520-5215
1520-5215
DOI:10.1021/jp305461z