Top Curr Chem (2016) 368: 377–414
DOI: 10.1007/128_2015_635
# Springer International Publishing Switzerland 2015
Published online: 1 July 2015
Absorption Spectroscopy, Emissive
Properties, and Ultrafast Intersystem
Crossing Processes in Transition Metal
Complexes: TD-DFT and Spin-Orbit
Coupling
Chantal Daniel
Abstract Absorption spectroscopy, emissive properties, and ultrafast intersystem
crossing processes in transition metal complexes are discussed in the light of recent
developments in time-dependent density functional theory (TD-DFT) , spin-orbit
coupling (SOC) effects, and non-adiabatic excited states dynamics. Methodological
highlights focus on spin-orbit and vibronic couplings and on the recent strategies
available for simulating ultra-fast intersystem crossings (ISC).
The role of SOC in the absorption spectroscopy of third-row transition metal
complexes is illustrated by two cases studies, namely Ir(III) phenyl pyridine and Re
(I) carbonyl bipyridine complexes.
The problem of luminescence decay in third-row transition metal complexes
handled by TD-DFT linear and quadratic response theories including SOC is
exemplified by three studies: (1) the phosphorescence of Ir(III) complexes from
the lowest triplet state; (2) the emissive properties of square planar Pt(II) complexes
with bidentate and terdentate ligands characterized by low-lying metal-to-ligandcharge-transfer (MLCT) and metal-centered (MC) states; and (3) the ultra-fast
luminescence decay of Re(I) carbonyl bipyridine halides via low-lying singlet
and triplet charge transfer states delocalized over the bipyridine and the halide
ligands.
Ultrafast ISC occurring in spin crossover [Fe (bpy) 3 ]
2+ , in [Ru (bpy) 3 ]
2+ , and
[Re (Br)(CO) 3 (bpy] complexes are deciphered thanks to recent developments based
on various approaches, namely non-radiative rate theory within the Condon approximation, non-adiabatic surface hopping molecular dynamics, and quantum wave
packet dynamics propagation.
C. Daniel (*)
Laboratoire de Chimie Quantique, Institut de Chimie UMR 7177 CNRS/Universite ´ de
Strasbourg, 1 Rue Blaise Pascal BP 296/R8, F-67008 Strasbourg Cedex, France
e-mail: c.daniel@unistra.fr
DOI: 10.1007/128_2015_635
# Springer International Publishing Switzerland 2015
Published online: 1 July 2015
Absorption Spectroscopy, Emissive
Properties, and Ultrafast Intersystem
Crossing Processes in Transition Metal
Complexes: TD-DFT and Spin-Orbit
Coupling
Chantal Daniel
Abstract Absorption spectroscopy, emissive properties, and ultrafast intersystem
crossing processes in transition metal complexes are discussed in the light of recent
developments in time-dependent density functional theory (TD-DFT) , spin-orbit
coupling (SOC) effects, and non-adiabatic excited states dynamics. Methodological
highlights focus on spin-orbit and vibronic couplings and on the recent strategies
available for simulating ultra-fast intersystem crossings (ISC).
The role of SOC in the absorption spectroscopy of third-row transition metal
complexes is illustrated by two cases studies, namely Ir(III) phenyl pyridine and Re
(I) carbonyl bipyridine complexes.
The problem of luminescence decay in third-row transition metal complexes
handled by TD-DFT linear and quadratic response theories including SOC is
exemplified by three studies: (1) the phosphorescence of Ir(III) complexes from
the lowest triplet state; (2) the emissive properties of square planar Pt(II) complexes
with bidentate and terdentate ligands characterized by low-lying metal-to-ligandcharge-transfer (MLCT) and metal-centered (MC) states; and (3) the ultra-fast
luminescence decay of Re(I) carbonyl bipyridine halides via low-lying singlet
and triplet charge transfer states delocalized over the bipyridine and the halide
ligands.
Ultrafast ISC occurring in spin crossover [Fe (bpy) 3 ]
2+ , in [Ru (bpy) 3 ]
2+ , and
[Re (Br)(CO) 3 (bpy] complexes are deciphered thanks to recent developments based
on various approaches, namely non-radiative rate theory within the Condon approximation, non-adiabatic surface hopping molecular dynamics, and quantum wave
packet dynamics propagation.
C. Daniel (*)
Laboratoire de Chimie Quantique, Institut de Chimie UMR 7177 CNRS/Universite ´ de
Strasbourg, 1 Rue Blaise Pascal BP 296/R8, F-67008 Strasbourg Cedex, France
e-mail: c.daniel@unistra.fr