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Jablonski Diagram
electronic ground state
A F
P
en
erg
y
IC
ISC
IC
S0
S1
S2
Sn
(ro)-vibrationalstates of el. excited states
T1
T2
A = photon absorptionF = fluorescenceP = phosphorescenceS = singlet stateT = triplet stateIC = internal conversionISC = 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 (Oh)
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 complexesSquare-planar complexes (D4h)
From: Yves Jean “Molecular Orbitals of Transition Metal Complexes”
Interactions of the d-block in transition metal complexesTetrahedral complexes (Td)
Crystal and Solution Spectra of Permanganate
aq. solution, 100 M
KMnO4 in KClO4 @ 4 K
J. Houmøller et al., CPC 13 (2013) 1133
Permanganate
1T2• Jahn-Teller distortion in excited states (C3v, C2v, D2d)• extensive vibronic coupling in 2T2 and 3T2 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
