Theoretical analysis of low-lying charge transfer states in [Ru(X) (Me)(CO)2(Me-DAB)] (X = Cl, I; DAB=1,4-diaza-1,3-butadiene) complexes by TDDFT and CASSCF/CASPT2 methods

被引:23
作者
Ben Amor, N.
Zalis, S.
Daniel, C.
机构
[1] Univ Strasbourg, CNRS, Inst Le Bel, UMR 7551,Lab Quim Quant, F-67000 Strasbourg, France
[2] Acad Sci Czech Republ, J Heyrovsky Inst Phys Chem, CR-18223 Prague 8, Czech Republic
关键词
ruthenium alpha-diimine complexes; excited states; ab initio; density functional theory;
D O I
10.1002/qua.21041
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The near-ultraviolet (UV)/visible electronic spectroscopy of [Ru(X)(Me)(CO)(2)(Me-DAB)] (X=Cl or I; DAB=1,4-diaza-1,3-butadiene), model complexes for a series of alpha-diimme halide complexes of ruthenium is investigated by means of time-dependent density functional theory (TDDFT) and complete active space self-consistent field/CAS second-order perturbation theory (CASSCF/CASPT2) methods. The convergence on the calculated transition energies to the low-lying metal-to-ligand-charge-transfer (MLCT), X-to-ligand-charge-transfer (XLCT) with X a halide ligand) or sigma-bond-to-ligand-charge-transfer (SBLCT) is analyzed for both methods with respect to various methodological aspects: basis set effects and functional influence on the TDDFT results versus the influence of the size and quality of the CASSCF and of the level of the perturbational treatment (single-state or multi-state) on the CASSCF/ CASPT2 transition energies. On the basis of these accurate calculations, it is shown that whereas the lowest singlet state can be assigned to a nearly pure XLCT state in [Ru(l)(Me)(CO)2(Me-DAB)], its character is mainly MLCT in [Ru(Cl)(Me)(CO)2(MeDAB)], in agreement with time-resolved emission/infrared (IR) and resonance Raman experimental data. The experimental bands are well reproduced by the CASSCF/CASPT2 calculations despite the difficulty at converging to stable transition energies when enlarging the CASSCE The TDDFT transitions energies are affected dramatically by the percentage of Hartree-Fock exchange in the hybrid functional. (C) 2006 Wiley Periodicals, Inc.
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收藏
页码:2458 / 2469
页数:12
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