Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+
✍ Scribed by Radka Baková; Majed Chergui; Chantal Daniel; Antonín Vlček Jr.; Stanislav Záliš
- Book ID
- 104011111
- Publisher
- Elsevier Science
- Year
- 2011
- Tongue
- English
- Weight
- 989 KB
- Volume
- 255
- Category
- Article
- ISSN
- 0010-8545
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✦ Synopsis
Spin-orbit coupling (SOC) is an essential factor in photophysics of heavy transition metal complexes. By enabling efficient population of the lowest triplet state and its strong emission, it gives rise to a very interesting photophysical behavior and underlies photonic applications such as organic light emitting diodes (OLED) or luminescent imaging agents. SOC affects excitedstate characters, relaxation dynamics, radiative and nonradiative decay pathways, as well as Abbreviations: ADF, Amsterdam Density Functional (quantum chemistry software package); bpy, 2,2 -bipyridine; C ∧ N, cyclometallated ligands coordinated by an aromatic carbon and nitrogen atoms; CASSCF, complete active space self-consistent field (computational technique); COSMO, conductor like screening model (describing solvent in DFT); DFT, density functional theory; DMF, N,N-dimethylformamide; dmp, 4,7-dimethyl-1,10-phenanthroline; imH, imidazole; IL, intraligand excited state, also called LC (ligand-centered); ISC, intersystem crossing; IVR, intramolecular vibrational reorganization; KS, Kohn-Sham; LCAO, linear combination of atomic orbitals; LF, ligand field excited state, also called MC (metal-centered); LLCT, ligand to ligand charge transfer; MLCT, metal to ligand charge transfer; MOLCAS, quantum chemistry software package; MS-CASPT2, multistate complete active space perturbation theory; N ∧ N, ␣-diimine ligands (usually polypyridines); OLED, organic light-emitting diode; phen, 1,10-phenanthroline; ppy, 2-phenyl-pyridine; RASSI-SO, restricted active space state interaction including SOC; SA-CASSCF, state average CASSCF; SO, spin-orbit; SOC, spin-orbit coupling; TDDFT, time-dependent DFT; thpy, 2-(2-thienyl)-pyridine; TRIR, time-resolved IR spectroscopy; UKS, unrestricted Kohn-Sham (DFT technique to calculate open-shell systems in terms of ␣,  spinorbitals).