Electronic Spectra and Transition Metal Complexes
Chapter 11: Electronic Spectra
Why are absorption spectra bands instead of lines?
•
Ground and excited state energy wells.
•
Electronic, vibrational, rotational and solvent transitions.
Electronic states of free ions.
Quantum numbers of multielectron atoms. Microstates.
Draw all microstates for a p
2
configuration.
(15 of them)
m
l
m
l
+1 0 -1
+1 0 -1
Electronic states of free ions.
Quantum numbers of multielectron atoms. Microstates.
Preview: d-d Transitions for transition metal complexes
Since octahedral compounds all seem to have only d-d
transitions that must be Laporte forbidden, why are they
colored?
Correlation diagram for
free ions and complexes.
Example: d
2
ion
Tanabe-Sugano Diagrams
Example: d
2
Tanabe-Sugano Diagrams: Example V(H
2
O)
6
3+
The interesting d
5
case:
Charge Transfer Transitions: LMCT
Charge Transfer Transitions: MLCT
Colors and Spectroscopy of Transition Metal Complexes
Why is:
1.
Mn
2+
(aq) colorless
2.
Cu
2+
(aq) less deeply blue colored than Cu(NH
3
)
4
2+
3.
Zn
2+
(aq) colorless
4.
MnO
4
-
deeply colored
5.
W(CO)
6
colorless
Mn
2+
(aq) MnO
4
-
Pi Acceptor Ligands and spectroscopy: CO, CN
-
, pyridine
Photophysics vs. Photochemistry
Ru(bpy)
3
2+
vs. Ru(py)
2
(bpy)
2
2+
Ru(py)
2
(bpy)
2
2+
Explore the world of electronic spectra, absorption bands, and transition metal complexes through various diagrams and explanations covering topics like d-d transitions, free ions, microstates, and charge transfer transitions. Discover the reasons behind the coloring of octahedral compounds despite Laporte forbidden transitions.
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Presentation Transcript
Chapter 11: Electronic Spectra hc = h = E
Why are absorption spectra bands instead of lines? Ground and excited state energy wells. Electronic, vibrational, rotational and solvent transitions.
Electronic states of free ions. Quantum numbers of multielectron atoms. Microstates. Draw all microstates for a p2 configuration. (15 of them) ml +1 0 -1 +1 0 -1 ml
Electronic states of free ions. Quantum numbers of multielectron atoms. Microstates.
Since octahedral compounds all seem to have only d-d transitions that must be Laporte forbidden, why are they colored?
Correlation diagram for free ions and complexes. Example: d2 ion
Tanabe-Sugano Diagrams Example: d2
Why is: 1. Mn2+(aq) colorless 2. Cu2+(aq) less deeply blue colored than Cu(NH3)42+ 3. Zn2+(aq) colorless 4. MnO4- deeply colored 5. W(CO)6 colorless
Mn2+(aq) MnO4-
Photophysics vs. Photochemistry Ru(bpy)32+ vs. Ru(py)2(bpy)22+
