title: Description of excited states in [Re(Imidazole)(CO)3 (Phen)](+) including solvent and spin-orbit coupling effects: Density functional theory versus multiconfigurational wavefunction approach.
abstract: The low-lying electronic excited states of [Re(imidazole)(CO)3 (phen)](+) (phen = 1,10-phenanthroline) ranging between 420 nm and 330 nm have been calculated by means of relativistic spin-orbit time-dependent density functional theory (TD-DFT) and wavefunction approaches (state-average-CASSCF/CASPT2). A direct comparison between the theoretical absorption spectra obtained with different methods including SOC and solvent corrections for water points to the difficulties at describing on the same footing the bands generated by metal-to-ligand charge transfer (MLCT), intraligand (IL) transition, and ligand-to-Ligand- charge transfer (LLCT). While TD-DFT and three-roots-state-average CASSCF (10,10) reproduce rather well the lowest broad MLCT band observed in the experimental spectrum between 420 nm and 330 nm, more flexible wavefunctions enlarged either by the number of roots or by the number of active orbitals and electrons destabilize the MLCT states by introducing IL and LLCT character in the lowest part of the absorption spectrum. © 2016 Wiley Periodicals, Inc.
authors: Laboratoire De Chimie Quantique, Institut De Chimie Strasbourg, UMR7177 CNRS/Université De Strasbourg, 1 Rue Blaise Pascal BP296/R8, Strasbourg, F-67008, France.
authors: Maria
authors: M
authors: Fumanal
authors: Laboratoire De Chimie Quantique, Institut De Chimie Strasbourg, UMR7177 CNRS/Université De Strasbourg, 1 Rue Blaise Pascal BP296/R8, Strasbourg, F-67008, France. c.daniel@unistra.fr.
authors: Chantal
authors: C
authors: Daniel
keywords: absorption spectroscopy; density functional theory; quantum chemistry; rhenium (I) complexes; spin-orbit coupling; wave function