North Carolina State University Department of Chemistry
Chemistry 703: Symmetry, Molecular Orbital Theory, and Optical
Spectroscopy of Inorganic Compounds
Spring 2013
Monday, Wednesday 10:15-11:30, Dabney 623
Instructor: David A. Shultz (363C Partners III
Chapter VII. Electronic Spectroscopy: Part II. Examples
VII.3 Mixed Valence Species
1896: Werner noted compounds containing Pt in two oxidation
states were darker in color than those containing Pt in one oxidation
state.
1950: the color in these complexes
Chapter VII. Electronic Spectroscopy: Part II. Examples
VII.3 Mixed Valence Species
1896: Werner noted compounds containing Pt in two oxidation states
were darker in color than those containing Pt in one oxidation state.
1950: the color in these complexes
Chapter VI. Electronic Spectroscopy.
Part I. Theory
Tot assumed separable, Tot = MOspin vib = | n>| s>| v>
Overall orbital wavefunction is the product of occupied one
electron wavefunctions, MO: MO = MO
If approximations either fail or are insufficient
Chapter VI. Electronic Spectroscopy.
Part I. Theory
Tot assumed separable, Tot = MOspin vib = nsv
Overall orbital wavefunction is the product of occupied one
electron wavefunctions, MO: MO = MO
If approximations either fail or are insufficient, then co
Chapter V. Vibrational Spectroscopy Part II. Examples
V.1 The effect of mass
ion
s (Cl-M-Cl)
(Cl-M-Cl)
a (Cl-M-Cl)
CuCl2-
300
109
405
AuCl2-
329
120,112*
350
* Degeneracy lifted by solid state effects, see section IV.14.
In going from CuI to AuI, the s i
Chapter V. Vibrational Spectroscopy Part II. Examples
V.1 The effect of mass
ion
s (Cl-M-Cl)
(Cl-M-Cl)
a (Cl-M-Cl)
CuCl2-
300
109
405
AuCl2-
329
120,112*
350
* Degeneracy lifted by solid state effects, see section IV.14.
In going from CuI to AuI, the s i
Chapter IV. Vibrational Spectroscopy: Part I. Theory
IV.1 The Harmonic Oscillator - a classical view
re
M
r
m
M
m
MaM = F = -k(r-re) = F = mam
the internal coordinate, Q,
Q = (r-re)
The restoring force (F) can then be written as,
F = -kQ
Force is the grad
Chapter IV. Vibrational Spectroscopy: Part I. Theory
IV.1 The Harmonic Oscillator - a classical view
re
M
r
m
M
m
MaM = F = -k(r-re) = F = mam
the internal coordinate, Q,
Q = (r-re)
The restoring force (F) can then be written as,
F = -kQ
Force is the grad
Chapter III. General Spectroscopic Considerations
III.1 Electromagnetic Radiation
Spectroscopy is the study of the interaction of electromagnetic
radiation with matter. Different types of EMR are displayed in the
electromagnetic spectrum:
IR
UV
log
log
Chapter III. General Spectroscopic Considerations
III.1 Electromagnetic Radiation
Spectroscopy is the study of the interaction of electromagnetic
radiation with matter. Different types of EMR are displayed in the
electromagnetic spectrum:
IR
UV
log n
log
Chapter II - Molecular Orbital Theory
II.1 Quantum Theory: a brief tour
Perhaps the most encountered quantum mechanical
expression is the Schrdinger equation:
H n = En n
Eq II.1
H is the Hamiltonian or energy operator
n is the stationary state wavefunctio
Chapter II - Molecular Orbital Theory
II.1 Quantum Theory: a brief tour
Perhaps the most encountered quantum mechanical
expression is the Schrdinger equation:
Hn = Enn
Eq II.1
H is the Hamiltonian or energy operator
n is the stationary state wavefunction
Symmetry: mutual relation of the parts of something
in respect to magnitude, shape and position
H = E
Symmetry in mathematics
1x1=1
11 x 11 = 121
111 x 111 = 12321
1111 x 1111 = 1234321
11111 x 11111 = 123454321
111111 x 111111 = 12345654321
1111111 x 111
Symmetry: mutual relation of the parts of something
in respect to magnitude, shape and position
H = E
Symmetry in mathematics
1x1=1
11 x 11 = 121
111 x 111 = 12321
1111 x 1111 = 1234321
11111 x 11111 = 123454321
111111 x 111111 = 12345654321
1111111 x 11