Topics in Current Chemistry

Top Curr Chem (2004) 241:119--165
DOI 10.1007/b96862
Springer-Verlag 2004
Electronic Spectroscopy and Photoreactivity
of Transition Metal Complexes:
Quantum Chemistry and Wave Packet Dynamics
Chantal Daniel (*)
Laboratoire de Chimie Quantique, UMR 7551 CNRS/UniversitØ Louis Pasteur,
4 Rue Blaise Pascal, 67000 Strasbourg, France
daniel@quantix.u-strasbg.fr
1 Introduction .................................... 120
2 Quantum Chemical Methods ........................... 122
2.1 Basis Sets Effects and Effective Core Potentials ................. 123
2.2 Electron Correlation ................................ 124
2.3 Relativistic and Spin-Orbit Effects ........................ 126
2.4 Computational Methods .............................. 127
2.4.1 Variational Methods ................................ 128
2.4.2 Second Order Perturbational Approach ..................... 130
2.4.3 Cluster Expansion Methods ............................ 131
2.4.4 Density Functional Based Methods ........................ 132
2.5 Potential Energy Surfaces ............................. 133
2.6 Non-Adiabatic Processes ............................. 135
2.6.1 Adiabatic Representation ............................. 136
2.6.2 Diabatic Representation .............................. 136
2.6.3 Diabatisation .................................... 137
2.7 Wave Packet Propagations. ............................ 138
3 Electronic Spectroscopy .............................. 140
3.1 Electronic Spectroscopy of Transition Metal Carbonyls. ............ 141
3.1.1 Ni(CO) 4, Cr(CO) 6, HM(CO) 5 (M=Mn, Re) and Mn 2(CO) 10 ........... 141
3.1.2 Mixed-Ligand Carbonyls W(CO)5L (L=Pyridine, CyanoPyridine) ....... 143
3.2 Metal-to-Ligand-Charge-Transfer a-Diimine Complexes ............ 145
3.2.1 Near UV-visible Absorption Spectra of [Ru(E)(E 0 )(CO)2(iPr-DAB)]
(E=E 0 =SnPh 3 or Cl; E=SnPh 3 or Cl, E 0 =CH 3;
iPr-DAB=N,N 0 -diisopropyl-1,4-diaza-1,3-butadiene) .............. 145
3.2.2 Electronic Spectroscopy of [M(R)(CO) 3(H-DAB)]
(M=Mn, Re; R=H, Ethyl, H-DAB=1,4-diaza-1,3-butadiene) .......... 147
3.3 Cyclometalated Complexes ............................ 149
3.3.1 Electronic Spectra of M(2-thienylpyridine)2 (M=Pd, Pt) Complexes:
a CASSCF/CASPT2 Study ............................. 149
3.3.2 Excited Electronic States in Phenylpyridine Ir (III) Complexes:
A TD-DFT Study .................................. 150
3.4 Spin-Orbit Effects on the Electronic Spectroscopy ............... 152
3.4.1 The Octahedral RhCl 6 3Ÿ Complex ........................ 152
3.4.2 Trischelated Diketonato Complexes of Trivalent Chromium .......... 153
4 Photoreactivity. .................................. 154