Jablonski Diagram electronic ground state A F P energy IC ISC IC S0S0 S1S1 S2S2 SnSn (ro)-vibrational states of el. excited states T1T1 T2T2 A = photon absorption F = fluorescence P = phosphorescence S = singlet state T = triplet state IC = internal conversion ISC = inter-system crossing

Typical “Mirror Image” Behavior of Fluorescence and Absorption (From P. Atkins et al.”Physical Chemistry”)

(From A. Zewail’s Nobel Lecture 1999)

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes”  -bonds in transition metal complexes

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes” Interactions of the d-block in transition metal complexes

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes” Interactions of the d-block in transition metal complexes

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes” Interactions of the d-block in octahedral transition metal complexes (O h ) depends on  - and  -interactions d-d transitions are Laporte-forbidden (both are gerade orbitals)

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes” Interactions of the d-block in transition metal complexes Square-planar complexes (D 4h )

From: Yves Jean “Molecular Orbitals of Transition Metal Complexes” Interactions of the d-block in transition metal complexes Tetrahedral complexes (T d )

Crystal and Solution Spectra of Permanganate aq. solution, 100  M KMnO 4 in KClO 4 K J. Houmøller et al., CPC 13 (2013) 1133

Permanganate 1T 2 Jahn-Teller distortion in excited states (C 3v, C 2v, D 2d ) extensive vibronic coupling in 2T 2 and 3T 2 states calculated excitation energies problematic assignments of transitions strongly debated until recently (Nooijen 2005, Ziegler 2011/2012)

From G. Herzberg, Molecular Spectra and Molecular Structure, Vol. III