Chem 213: Advanced Ligand Field Theory

Todd Gingrich
May 6, 2008
D. Introduction to Electronic Spectra
1. (a) The following transitions could occur in an octahedral d3 complex. Which of these are formally
forbidden and why? Make an order of magnitude estimate of the extinction coecient and oscillator strength of each transition. Propose mechanisms by which each transition could gain intensity.
i. 4 A2g 4 T2u is formally allowed. It is clearly spin allowed, and it is also orbitally allowed
because the triple product A2g T1u T2u = A1g Eg T1g T2g contains the totally
symmetric representation. Thus we expect  10, 000M 1cm1 with an oscillator strength
of f 1.
ii. 4 A2g 4 T2g is formally orbitally-forbidden because A2g T1u T2g has u parity and therefore
does not contain a totally symmetric component. Thus we expect  100 with f 0.01.
This transistion could gain intensity by coupling to vibration with u parity.
4
iii. A2g 4 T1u is formally orbitally-forbidden since A2g T1u T1u = A2g Eg T1g T2g ,
which does not contain the A1g representation. Thus we expect  100 with f 0.01. This
transition could gain intensity by coupling to a A2g , Eg , T1g , or T2g vibration.
iv. 4 A2g 2 Eg is spin-forbidden and orbitally-forbidden since A2g T1u Eg = T1u T2u .
Therefore we expect  1 and f 104 . This transition could gain intensity if spinorbit coupling were increased, which would occur in a heavier metal. The intensity would
also increase if the transition were to become orbitally-allowed by coupling to a T1g or T2g
vibration.
v. 4 A2g 2 T2u is spin forbidden (but orbitally-allowed like (i)). We expect  1 and f 104 ,
but if comparing the intensities of (iv) and (v) we note that (iv) should be weaker as it is
doubly disallowed. This transition could be more intense if spin-orbit coupling is strengthened.
(b) Determine the symmetries of the normal modes of vibration of an octahedral complex. Use these to
justify intensity gains in the transitions of part (a) via vibronic interactions based on these modes.
First we seek the symmetries of the normal modes of vibration. We arbitrarily x the location of the metal atom (hereby removing the three degrees of translational freedom). Now we
consider the action of each of our symmetry elements on the basis set formed by local (x, y, z)
axis centered on each ligand atom. We record the traces for this representation of the group that
we call tot where by total we mean rotational plus vibrational. The rotations (rot ) transform
as T1g based on a character table. Subtracting these traces out we can obtain the traces of the
vibrational representation, vib .
Oh
tot
rot
vib

E
18
3
15

8C3
0
0
0

6C2
0
-1
1

3C2 (=C24 )
-2
-1
-1

6C4
2
1
1

i
0
3
-3

6S4
0
1
-1

8S6
0
0
0

3h
4
-1
5

6d
2
-1
3

After applying the Great Orthogonality Theorem, we see that vib = A1g Eg T2g 2T1u T2u .
The T1u and T2u vibrations can couple with the 4 A2g 4 T2g electronic transition to increase the
intensity of the band. The Eg and T2g vibrations could couple with the 4 A2g 4 T2u electronic
transition to increase the intensity.

2. Absorption spectra of Cr(III) complexes are readily analyzed using the ligand eld theory derived in
parts A-C.
(a) Summarize the atomic selection rules. The absorption of a free Cr(III) ion shows a weak band at
about 14,000 cm1 . Explain.
Atomic transitions are formally allowed i S = 0 and L = 0, 1 (excluding L = 0 0).
For a rst row transition metal such as Chromium, the spin-orbit coupling is weak so the spin
orthogonality is close to rigorously true. Thus the weak band at 14,000 cm1 must come from
an exitation from the ground 4 F ground term to an exited quartet term. There is only one such
transition in a d3 free ion conguration, so we attribute the 14,000 cm1 band to the 4 F 4 P
transition. This transition is formally disallowed as L = 2, but the dipole approximation of
light breaks down leading to the weak band.
(b) The electronic spectra of four Cr(III) complexes, CrLn
6 , are summarized below. Assign the bands
(assuming they are all allowed transitions). Estimate Dq and B values from the Tanabe-Sugano
diagram. Use these values to calculate the positions of each band for each of the complexes. Draw
an energy level diagram showing the levels for all four compounds. On the basis of these results,
order the ligands in the table in the spectroschemical series and the nephelauxetic series.
L
H2 O
F
Urea
CN

(cm1 )
24,500
22,700
22,600
32,500

17,400
14,900
16,150
26,600

38,000
34,400
34,400
?

From low to high energy we assign the bands as: 4 T2g 4 A2g , 4 T1g 4 A2g , and 4 T1g 4 A2g .
Equations 30 and 31 in Problem Set C give analytic expressions for the transition energies with
respect to Dq and B. There is some ambiguity in our assignment of Dq and B since there are
two parameters and three data points. We use the low energy band to solve for Dq. We then use
that value to solve for B based on the high and low energy T1g bands. The two dierent values
of B are averaged to give:
L
H2 O
F
Urea
CN

Dq(cm1 )
1,740
1,490
1,615
2,660

B(cm1 )
686
843
562
529

These parameters lead to bands which are consistent with the reported values:
L
H2 O
F
Urea
CN

A2g 4 T2g
17,400
14,900
16,150
26,600

A2g 4 T1g
24,300
22,400
21,950
32,500

A2g 4 T1g
38,200
34,900
34,950
55,250

In Figure 1 we can also plot (to scale) the energies of each state (neglecting the 3A term that all
states share).
From the calculated values of B and Dq, we can order the ligands with respect to the spectrochemical series (Dq) and the nephelauxetic series (B).
Spectrochemical Series: F < Urea < H2 O < CN
Nephelauxetic Series: CN < Urea < H2 O < F
3

20000
4

T1g

T1g

T2g

A2g

10000

Energy (cm1 )

10000

20000

30000

40000
F

H2 O

Urea

CN

Figure 1: Cr(III) Ligand Field Energies for Various Ligands.

(c) Read the paper by Krause, Trabjerg, and Ballhausen (Chem. Phys. Lett. 1969, 3, 297-299) and
comment critically on the signicance of this two photon experiment.
The two-photon experiment of Krause et. al. provides insight into the structure of the doublet
manifold of a Cr(III) complex. A ash lamp is used to excite the complex into the 2 Eg state.
Immediately after this ash, a spectrum is taken (the second photon) to record transitions from
the 2 Eg state into higher energy doublet states. A spectrum taken without the initial ash is
used for background subtraction to eliminate the quartet excitations. There are two aspects of
the experiment that seem a little concerning. First, there is a shoulder at 25,000 cm1 , which
could not be explained by a doublet-doublet transition, but matches the 4 A2g 4 T1g transition
exactly. This suggests that the background subtraction did not entirely eliminate the quartetquartet transitions. It is also unclear to me how the energy of initial ash excitation was controlled.
The authors assume that the ash excites into the 2 Eg state and not any of the higher energy
doublet states. This assumption demands justication.
(d) Read the paper by Witzke (Theoret. Chim. Acta. 1971, 20, 171-184). This is typical of eorts
aimed at parameterizing d-d spectra. Summarize the conclusions and general methodology.
For practical use the most important conclusion is that the ratio C/B = 4 is a good approximation
for the free ion, but for an ion in the presence of a ligand eld the ratio of C/B is not constant
and not necessarily 4. The constant ratio would only hold if the radial functions were not
complex-dependent. Full molecular orbital theory is really necessary to fully resolve this issue.
The paper also suggests that in order to better parameterize the d-d it requires a dierent B value
for the spin-allowed transitions compared to the spin-forbidden transitions. The paper starts by
discussing simple methodology (ie crude approximations). The method we used in part (b) of
this problem is employed as the simplest method for predicting spin-allowed transitions. For
spin-forbidden transitions the Tanabe-Sugano matrices (electrostatic matrices in the strong-eld
basis set) were diagonalized numerically and the values of B and C which matched the observed
absorptions most closely were used. If B and C held rigorous in these situations then there should
be a value of B and C that will predict each possible transition, but in general the curves for C
4

as a funciton of B do not converge on a point. This is a consequence of the fact that B and C
can only make sense as a linear combination of F2 and F4 which are integrals of d orbitals. In the
bonded compound, those orbitals change shape, demanding that a full molecular orbital approach
be employed to actually predict the energy levels. Nevertheless, Witzkes paper demonstrates
that the rough 3 parameter (, B, C) approach works fairly well.
(e) The absorption spectra of Cr(en)3+
and of the cis and trans isomers of Cr(en)2 (H2 O)3+
are
3
2
shown below. Assign the observed bands and identify which spectra correspond to the cis and
trans isomers. Explain.

Figure 2: Absorption Spectra of Cr(en)3+

(), cis-Cr(en)2 (H2 O)3+
(- - - -), and trans-Cr(en)2 (H2 O)3+
3
2
2
( ).
The assignment of the Cr(en)3+
spectra is straightforward. The low energy peak at 22, 000
3
cm1 is the 4 A2g 4 T2g transition while the higher energy peak at 27, 500 cm1 is the
4
A2g 4 T1g transition.
are more complicated. Section 5-c of Ballhausen treats the cis and trans
The Cr(en)2 (H2 O)3+
2
problem. The elds are expanded into the sum of cubic, tetragonal, and rhombic eld components. The tetragonal component causes the degeneracy of the cubic states to split most strongly,
so Ballhausen focuses on the eect of the cis/trans conguration on the strength of the tetragonal
component. It is shown that a trans complex will exhibit twice the tetragonal splitting as a cis
compound, so the broadened peak ( ) is taken to be the trans complex. In D4h symmetry we
must reassign these peaks with respect to the new point group. The Oh 4 A2g 4 T1g transition
splits into: 4 B1g 4 Eg (19, 500 cm1 ), 4 B1g 4 A2g (22, 500 cm1 ). Splitting of the Oh
4
A2g 4 T2g transition is not as pronounced in the spectrum, but some broadening is observed
as the transition splits into the two nondegenerate transitions: 4 B1g 4 Eg and 4 B1g 4 B2g .
Because the tetragonal splitting is so much weaker in the cis complex, the peaks do not really split, but some broadening is observed. As pointed out in Ballhausen, the ordering of the
excited states will switch (ie 4 Eg will lie above 4 A2g ).

3. (a) Briey discuss the stability of octahedral low- and high-spin d7 complexes.
d7 complexes with large O will be most stable sacricing the spin-pairing energy in order to
populate the (eg ) set with as few electrons as possible. Hence low-spin d7 complexes are most
stable for large splitting. If the splitting is small, then the cost of spin-pairing may exceed the cost
of moving another electron from the (t2g ) set into the (eg ) set. In these situations the high-spin
(t2g )5 (eg )2 conguration is favored.
(b) In both cases in (a), a distortion from Oh symmetry is predicted. Explain. What geometries
might you expect and how will the ground states be split? Comment on the relative magnitudes
of the splittings.
In the low spin case there is a single electron occupying the degenerate eg set so Jahn-Teller
splitting is expected. The splitting will be stong since the eg set points directly at the octahedral
ligands and therefore distortions can signicantly aect the overlap between eg orbitals and the
molecular orbitals. In the high spin case we expect Jahn-Teller distortion because there is a single
vacancy in the triply degenerate t2g set. The splitting of this t2g set will be signicantly smaller
than the low spin J-T splitting since distortions in geometry cannot strongly aect ligand-metal
orbital overlap integrals because the t2g orbitals do not point directly at the octahedral ligands.
The low spin distortion would distort into D4h geometry such that the dz2 level drops in energy and the dx2 y2 level rises. The d7 low spin ground state is 2 Eg , which in D4h symmetry
splits into 2 A1g 2 B1g . Because dz2 is lower in energy than dx2 y2 it is clear that the 2 A1g state
is lower in energy that the 2 B1g state. An axial distortion still maintains zero overlap of the t2g
orbitals with the ligand orbitals, so a J-T distortion in the high spin case will not be along the
C4 axis. Rather, the elongation would be along the C3 axis to give D3d symmetry. In that case
the 4 T1g ground state would be reduced to 4 A2 4 E  with 4 A2 lying lower in energy.
(c) Shown below are absorption spectra for Co(H2 O)2+
and CoCl2
in aqueous solution. Identify
6
4
which spectrum belongs to which compound. Explain.

2
Figure 3: Co(H2 O)2+
6 and CoCl4 in aqueous solution
9
Co(H2 O)2+
6 is the unstructured peak on the left because the peak is at higher energy. O = 4 T ,
2
so the lower energy peak is the tetrahedral complex: CoCl4 .

(d) The absorption spectra for two crystals of KCoF3 of dierent thickness at approximately 150 K
are shown below. What are the advantages of working at low-temperature and using crystalline
samples to study the spectroscopy of metal complexes?

Figure 4: Absorption spectra of two crystals of KCoF3 of dierent thicknesses at approximately 150 K
Assuming the two most intense features in this spectrum correspond to spin-allowed transitions,
assign these bands. Identify any other spin-allowed feature(s) and comment on their intensity.
Assuming the weak feature at 10, 000 cm1 is the lowest energy Eg term, determine values for
Dq, B, and C. Comment on these results. Comment on any remaining features in the spectrum.
Why does the broad spin-allowed band around 19, 200 cm1 appear structured?
Low temperatures and crystalline samples can allow one to resolve vibrational structure. These
samples are also adventageous since they eliminate coupling with the solvent and reorganization
eects.
We assume that the strongest three bands are the spin-allowed bands:
4

T1g 4 T2g
T1g 4 A2g
4
T1g 4 T1g

7200 cm1
15000 cm1
19000 cm1

The band at 15, 000 cm1 is weaker than the other two because the 4 A2g state has a smaller
degeneracy and the 4 T1g and 4 T2g states.
Because E(4 A2g ) = 12Dq 43B + 14C and E(4 T2g ) = 2Dq 43B + 14C, 10Dq can be obtained
as the dierence between the position of the 4 T1g 4 A2g band and the 4 T1g 4 T2g band.
Hence 
Dq = 7800 cm1 . Also the the energy dierence between the two 4 T1g states should

be 5 45B 2 + 36 Dq B + 20Dq 2 . Setting this equal to 19, 000 cm1 and solving for B gives
B = 880 cm1 . Finally, to nd C we must use the 2 Eg band at 10, 000 cm1 and use:

5
3
2
4
45B 2 + 36 Dq B + 20Dq 2
E( Eg ) E( T1g ) = 15Dq + B + 3C +
2
2
C = 3640 cm1
The small value of Dq is a result of the -donations of F1 ions, which makes the ligand eld
weaker. The values of B and C are quite typical. The structure in the peak at 19, 000 cm1 is
due to dierent vibronically excited modes. I was puzzled by additional weak featers at 17, 500
cm1 and 21, 500 cm1 . I consulted the original paper, which suggested that these peaks were
due to other doublet excitations.
7

4. The visible spectrum of VCl4

is strongly temperature dependent (see below). The positions of the
6
peak maxima at 77 K are 7, 200 cm1 , 11, 700 cm1 , and 19, 100 cm1 .

Figure 5: Visible spectrum of VCl4

6

(a) Assign the bands in the spectrum.

is a d3 compound with a 4 A2g ground state. The band at 7, 200 cm1 is due to the
VCl4
6
spin-forbidden 4 A2g 2 Eg transition. The band at 11, 700 cm1 is due to the 4 A2g 4 T2g
transition. The band at 19, 100 cm1 is due to the 4 A2g 4 T1g .
(b) Account for the temperature dependence of this spectrum.
The observed transitions are formally symmetry forbidden. The weak bands are possible through
vibronic coupling (see problem 1). As the vibronic coupling is weakened by lowering the temperature, the bands weaken. Additional, the absorption maximums blue-shift because there is less
vibrational energy, so the electronic energy must increase in order to compensate.

5. The ability to predict the relative intensities of electronic transitions available to molecular systems
often proves to be a useful tool when assigning an absorption spectrum. Selection rules derived from
quantum mechanical arguments provide a means of doing just that. However, it is important to remember that selection rules for a particular molecule in question are only as reliable as the wavefunctions
and approximations used to derive them. This problem will deal with the derivation of selection rules
for a hydrogen atom in a beam of plane polarized light. The methodology used here can be extended
to molecular systems as well.
A development of the equations describing the interaction of an atomic or molecular system with
the time-dependent electric and magnetic elds of an incident light beam usually beings with Fermis
golden rule:
2    2
(1)
Poj = 2  j G
 o  oj

By solving Maxwells equations along with the classical Hamiltonian for a charged particle moving in
an electric and magnetic eld it may be shown that the time-dependent perturbation found in (1) can
be written as:
 iQ
=

G
A
(2)
M
c

 is the vector potential produced by the time-dependent elds found in the incident radiation.
where A
 = A()uei c kr + A()uei c kr
A

(3)

Here k is the wave vector pointing in the direction of the propoagation of the light wave and u is the
unit vector pointing in the direction of the oscillating electric eld. If the wavefunctions j and o are
taken to be Born-Oppenheimer functions, then the sum over nuclear coordinates in (2) reduces to a
sum over electronic coordinates multiplied by some Frank-Condon factors. Using this idea and these
equations we have:
 
 2
 
2   

 
k
r
i
A ue c
 o  oj
(4)
Poj = 2  j 
 
  

Here the index runs over all electronic coordinates. Using (4) as a starting point, derive the selection
rules for electic dipole, magnetic dipole, and electric quadrupole allowed electronic transitions in a
hydrogen atom for light traveling in the z direction and polarized in the x direction.
Solution: Expanding out the exponential in (4) yields:
Poj

2
2


 
  
 2

 

 


 

 
j
A u  o + 
A u(i k r)  o  oj
 j

 

 
c

(5)

but k = z and u = x
, so the sums over the single hydrogen atoms electronic coordinates collapses
Poj

 

 2




 
2   


(i

z
)
o

+
j
j
A
A

 x c  o  oj
2   x 

(6)

Solving for when the rst matrix element is nonzero gives the electronic dipole selection rules. Lets
examine this matrix element more closely, making use of the fact that
[H, x] =

2
m x







nlm A  n l m
=
x
=
=

mA

nlm |[H, x]| nlm

2
mA
2
nlm |Hx xH| n l m 

mA
2 (En En )
nlm |x| nlm


which is nonzero i En = En n = n since the energy of the nth eigenstate is only dependent on n
in the Hydrogen atom. The rest of the electronic dipole selection rules arise from solving for when

nlm |x| nl m  = 0


2 4 1
(Y
Y11 )
x=r
2
3 1

We note that

Hence,


 



2 4

nlm |x| nl m  = r
( nlm Y11  nl m nlm Y11  nl m )
2
3


(7)

We recall that |nlm = Rn,l (r)Ylm (, ) = N Rn,l (r)Plm (cos )eim . From the exponential terms we
immediately see that:



Yml Y11 Yml  d = 0 unless m 1 = m

We also note that the character of an inversion is given by (i) = (1)l and so the character of the
inversion for a direct prodcut is only 1 if l + l is odd. We also note that Yml belongs to the irrep of the
full rotation group, l while Y11 belongs to 1 . We can take the direct product of these irreps to get
l 1 = (l+1) + l + (l1)
From this it is clear that the integral in (7) vanishes unless l 1 = l , giving the nal dipole selection
rule for x-polarized light.
Now we return to (6) and look at the second matrix element to see when it is zero. This matrix element
will give us the electric quadrupole and the magnetic dipole selection rules. We note that


2

[H, xz] =
+z
x
m
z
x
allowing us to write the second matrix element as:
 


 
 

iA  





=
o
+x
x
j A (i z ) o
j z
+ z
x c
2c
x
z
x
z 


 
 
iA   m

=
x
o
j  2 [H, xy] + z
2c

x
z 
 
  iA

iA   m




o
=
x
j  2 [H, xy]  o +
j  z
2c

2c
x
z 

(8)

The rst matrix element of (8) is recognized as the electric quadruople operator after H is applied to
the bra and ket respectively as in the electric dipole case. The second matrix element of (8) is actually

10

the matrix element of an angular momentum Jy , which is linearly proportional to the magnetic dipole
operator. Hence the electric quadrupole selection rules arise from solving for when:
< nlm|[H, xy]|n l m >= 0
Observe that
< nlm|[H, xy]|n l m >= (En En ) < nlm|xy|n l m >= (En En ) < nlm|xy|n l m >

(9)

which demands that n = n in order for the integral to not vanish. Additionally we can re-express y
with respect to the spherical harmonics:


2 4  1
Y1 + Y11
y = r
2
3
xy =


2  1 2
(Y1 ) + (Y11 )2
3

When we square Y11 there is a factor of e2im , which requires that m 2 = m for a nonvanishing integral. Also, the representation of the perturbation is now 1 1 which spans 2 1 0 1 2 .
So due to rotation group considerations, |l l | < 4. Also, due to the inversion considerations, l + l
must be even. This requires l = l or l 2 = l .
The magnetic dipole selection rules arise from solving for when:
< nlm|Jy |n l m >= 0
Jy is an axial pseudo-vector so it is g under inversion. Unlike the electric dipole selection rules this
requires that l = l . Re-expressing the matrix element with respect to the shift operators gives:
1
< nlm| (J+ + J )|nlm >
2
which is obviously nonzero i m 1 = m . This completes the selection rules for magnetic dipoles.

11

6. The Fe atom in the protein rubredoxin is thought to reside in a roughly tetrahedral environment
consisting of four mercaptide S atoms. The UV/Vis spectra of ferric and ferrous rubredoxin are
dominated by charge transfer bands. The d d bands were located in the near IR by Eaton and
Lovenberg (JACS 1970, 92, 7195-7198). Read this paper and answer the following questions:
(a) Briey describe why circular dichroism is as useful as absorption spectroscopy in locating the
ligand eld bands in this case. Explain the assignment of the band at 6250 cm1 .
Circular Dichroism (CD) provides a method to ensure that the feature at 6250 cm1 is an electronic transition. The 5 E 5 T transition is magnetic dipole allowed, so the fact that the band
shows up using CD conrms the assignment. Without the CD evidence, the feature could be
confused as a vibrational excitation (as was the case in ferric rubredoxin). Such vibrations, however, are not coupled together by the magnetic dipole moment, so the presence of the CD band
in ferrous rubredoxin indicates that there is actually an electronic transition at 6250 cm1 . This
band is assigned to the only spin-allowed transition: 5 E 5 T .
(b) The authors state that the other spectral data indicate that the Fe site symmetry may be less
that Td . Assuming a distortion leading to D2d symmetry can occur, how will the d orbitals split
in this lower symmetry environment? How many excited states would you expect? A transition
has been detected in Mossbauer experiments that does not correspond to an iron nuclear spin ip
(850 cm1 ). Which symmetry do you think is present in the protein? Explain.
In D2d symmetry, the e and t2 sets split out. The e set splits into the b1 symmetry x2 y 2 orbital
and the a1 symmetry z 2 orbital. The t2 set splits into the b2 symmetry xy orbital and the e
symmetry (yz, xz) orbitals. The ground state is a 5 A1 state with the b1 , a1 , b2 , and e sets all
singly occupied with alligned spins. A spin allowed excitation requires a promotion of an electron
into the other spin-alligned E orbital. This electron could originate from the b1 , a1 , or b2 orbital,
so there are three spin-allowed excited states corresponding to the following transitions:
x2 y 2
z2

(yz, xz)
(yz, xz)

xy

(yz, xz)

The rst of these two transitions are roughly equal in energy (both 6000cm1 ). The second
transition is essential the energy of the splitting of the t2 set from tetrahedral splitting. It is
conceivable that if the distortion is strong enough, this energy splitting could be several hundred wavenumbers. Hence, I suspect that the true symmetry is D2d and that the Mossbauer
experiments have revealed the splitting of the tetrahedral t2 set.

12

7. The rst two spin-allowed d-d transitions in three octahedral d6 low-spin cobalt(III) complexes have
been reported at the following positions:
Complex
Co(H2 O)3+
6
Co(NH3 )3+
6
Co(CN)3
6

1 (cm1 )
17,000
21,000
32,100

2 (cm1 )
25,000
29,000
38,500

Using the appropriate Tanabe-Sugano diagram in Figgis, predict the following transitions:
1

A1g

A1g ;1 A1g

T2g ;1 A1g

T2g

Careful examination of a 3 mm thick single crystal of K3 Co(CN)6 reveals a band at 26,000 cm1 ,
 = 0.25. Assign this band and obtain a value for C which xes the C/B ratio for low-spin Co(III). Recalculate the positions of the three spin-forbidden transitions mentioned above for all three complexes.
Would you expect to be able to observe more than one of these transitions? Appropriate strong-eld
energy expressions may be found in Table A29 of Grith (ignore conguration interactions). Finally
draw an energy level diagram illustrating how the three congurations (t62g ; t52g eg ; t42g e2g ) split into their
ligand eld states for hexacyanocobaltate and draw the transitions corresponding to the bands discussed above.
Solution: In a d6 complex the 1 A1g , 1 T1g , and 1 T2g energies (neglecting conuration interaction)
are:
E(1 A1g ) =
1

E( T1g ) =
E(1 T2g ) =

15A 17B + 13C 24Dq

15A 30B + 14C 14Dq
15A 14B + 14C 14Dq

So

So 16B = 2 1 B =

E(1 T1g ) E(1 A1g ) = 10Dq 13B + C

E(1 T2g ) E(1 A1g ) = 10Dq + 3B + C

2 1
16 .

We assume C/B = 4 to obtain:




2 1
1
1 + 9
= Dq
10
16

Hence we obtain
Complex
Co(H2 O)3+
6
Co(NH3 )3+
6
Co(CN)3
6

1 (cm1 )
17,000
21,000
32,100

2 (cm1 )
25,000
29,000
38,500

Dq (cm1 )
2150
2550
3570

B (cm1 )
500
500
400

Now we must nd the energy of the 3 A1g , 3 T2g , and 5 T2g states. The 3 A1g state can only arise from
the t32g e3g strong eld conguration. Table A29 in Griths gives the energy of this state (including the
9A 14B + 7C term from the hole formalism).
E(3 A1g ) = 15A 26B + 11C + 6Dq
13

The 3 T2g state can actually arise from several strong eld congurations, but we take the diagonal
matrix element of the lowest energy strong eld conguration
E(3 T2g ; t52g e1g ) = 15A 22B + 12C 14Dq
Similarly

E(5 T2g ; t42g e2g ) = 15A 35B + 7C 4Dq

From these energies we simply obtain the transitions energies:

E(1 A1g 3 A1g ) =
E(1 A1g 3 T2g ) =

30Dq 9B 2C
10Dq 5B C

E(1 A1g

20Dq 18B 6C

T2g ) =

So
Complex
Co(H2 O)3+
6
Co(NH3 )3+
6
Co(CN)3
6

A1g 3 A1g
34,500
42,500
64,600

A1g 3 T2g
17,000
21,000
32,100

A1g 5 T2g
22,000
30,000
54,600

The band at 26, 000 cm1 from the single crystal of K3 Co(CN)6 is due to the spin forbidden 1 A1g
3
T1g transition. From this we no longer have to use our C/B = 4 estimate. We can now solve for Dq,
B, and C in K3 Co(CN)6 and assume this C/B ratio for the other compounds.
Dq = 3425 cm1 , B = 400 cm1 , C = 3050 cm1

and

C/B = 7.6

Using this new value of C/B we get

Complex
Co(H2 O)3+
6
Co(NH3 )3+
6
Co(CN)3
6

A1g 1 T1g
17,000
21,000
32,100

A1g 1 T2g
25,000
29,000
38,500

A1g 3 A1g
27,250
35,250
58,800

A1g 3 T2g
13,375
17,375
29,200

A1g 5 T2g
7,500
15,500
43,000

A1g 3 T1g
9375
13,375
26,000

1
3
It appears that some of the bands should be observable. For example, in Co(NH3 )3+
6 , the A1g T2g
1
band is predicted to be at 17,375 cm . The  for this band would be very small though, making it
exceedingly dicult to see.

The energy level diagram demonstrating how the strong eld states split is given below. Only the
states we discussed are labeled.

14

t42g e2g
5
1

T2g
T2g

1
T1g
3
T2g
3
T1g

t52g e1g

A1g

t62g

Figure 6: Energy level diagram showing splitting of strong eld states in a d6 conguration

15

8. Gillespite is a rare silicate mineral which has gured prominently in the development of mineral spectroscopy. Read the paper by Burns, Clark, and Stone (Inorg. Chem. 1966, 5, 1268-1272) and answer
the following questions:
(a) Derive all of the possible spin-allowed electronic transitions from the ground state.
We treat the problem as having D4h symmetry. In this point group the d orbitals split into
a1g , eg , b2g , and b1g sets corresponding to orbitals which are dominanted by dz2 , (dxz , dyz ), dxy , and
dx2 y2 orbitals respectively. The paper shows that the ordering of these orbitals from low to high
energy are as listed. The paper also indicates that a high-spin ground state is observed. Hence the
ground state is the 5 A1g state corresponding to the conguration (dz2 )2 (dxz )1 (dyz )1 (dxy )1 (dx2 y2 )1 .
The spin accessible excited states will all be have a basic (dz2 )1 (dxz )1 (dyz )1 (dxy )1 (dx2 y2 )1 conguration with the sixth electron in each of the possible orbitals. Because the half-lled conguration
behaves as A1g , the spin-allowed excited states are just given by
A1g eg

= Eg

A1g b2g

= B2g

A1g b1g

= B1g

Thus the spin allowed transitions are 5 A1g

Eg , 5 A1g

B2g , and 5 A1g 5 B1g .

(b) Assume it is reasonable to consider only the local environment of the iron site and determine the
symmetries of the FeO4 vibrations. Do you think this assumption is reasonable?
We consider local x, y, and z coordinate systems on each of the 4 planar O atoms of the FeO4
unit. We neglect the axes on the Fe atom since these simply give translational motion. It is a
simple exercise to show that
D4h
tot
rot
vib

E
12
3
9

2C4
0
1
-1

C2
0
-1
1

2C2
-2
-1
-1

2C2
0
-1
1

i
0
3
-3

2S4
0
1
-1

h
4
-1
5

2v
2
-1
3

2d
0
-1
1

Applying the great orthogonality theorem yields vib = A1g B1g B2g A2u B2u 2Eu
(c) Derive the assignments and polarizations which are reported in Table II of the paper.
I will only derive the transitions in the table from the 5 A1g ground state since these are the transitions which were observed. In D4h the electric dipole vector can transform as Eu in the case of
(x, y) or as A2u in the case of z polarized light. For parallely polarized light, the electric dipole
transforms as A2u . In order for a transition to be allowed, it must couple to an ungerade vibration to overcome the Laporte selection rules. Since the ground state is A1g , a parallel transition
is allowed i X A2u Y = A1g where X is the excited state and Y is the representation of
the vibration. First we consider the parallel 5 A1g 5 Eg transition. Note that Eg A2u = Eu
and Eu Eu contains A1g , so the 5 A1g 5 Eg transtion is allowed if coupled with an Eu vibration.
Now we consdier 5 A1g 5 B2g . Note that B2g A2u = B1u . So in order to be allowed this would
have to couple to a B1u vibration, but there is no B1u vibration, making this transition forbidden.
Finally we consider 5 A1g 5 B1g . This is very similar to the case before except now we require
a B2u vibration, which is present.
Next we consider the perpendicular transitions, which make use of x and y polarized light that
transforms as Eu . The 5 A1g 5 Eg transition can actually be allowed through two dierent
16

vibrations since Eg Eu = A1u A2u B1u B2u . A A1u , A2u , B1u , or B2u vibration could
couple to these in order to give rise to an overall A1g matrix element. However only A2u and B2u
vibrations are present.
It is also straightforward to see that 5 A1g 5 B2g and 5 A1g 5 B1g are allowed if coupled to
Eu vibrations since:
Bng Eu Eu = Eu Eu = A1g A2g B1g B2g
This completes the derivation of Table II.

17

9. In addition to an absorption spectrum, the emission spectrum of a metal complex yields useful information about transitions between ground states and low-lying excited states. Emission from a transition
metal copmlex with an unlled d shell generally occurs from the lowest electronic excited state in the
molecule or from those states that can achieve a signciant Boltzmann population relative to the lowest
excited state. In problem 2 of this set, the absorption spectra of Cr(III) complexes were discussed.
In this problem the absorption and emission behavior of octahedral Cr(III) will be linked together
by potential energy surface considerations. Background material may be found in N.J. Turro Modern
Molecular Photochemistry, pp. 52-96.
(a) Excitation from the 4 A2g ground state into one of the spin-allowed 4 Tng excited states is followed by rapid internal conversion and vibrational relaxation inot the zeroth vibrational level of
the 4 T2g term. From this point, two main photophysical processes occur, namely uorescence
or intersystem crossing (ISC) into the 2 Eg term from which phosphorescence is observed. This
emission is not Stokes shifted; it overlaps the very weak corresponding absorption band. This
leads to an unusual situation in that the uorescence is found to the red of the phosphorescence.
The situation is illustrated in the following Jablonski diagram. A typical spectra is also shown.
Construct qualitative plots of energy vs. Q (a totally symmetric nuclear coordinate) in which

the intersections, energy gaps, and widths of the PE surfaces for the 4 A2g , 4 T2g , 2 Eg , and 4 T1g
terms are illustrated. Keeping in mind that each Dq/B value in a Tanabe-Sugano diagram corresponds to a dierent set of nuclear coordinates, provide plots for three cases: (a)Dq/B < 2.1;
(b) Dq/B = 2.1; (c) Dq/B > 2.1. Use the appropriate Tanabe-Sugano diagram in Figgis.
Solution: Note that at Dq/B = 2.1, E(4 T2g ) = E(2 Eg ). This equality is for a xed value of
Q, so it is only for the vertical transition. We approximate the quartet terms as all having the
same width, and the doublet term is slightly wider.

T1g
2

T1g

T2g

T2g

A2g

Eg

18

Eg

A2g

Dq/B = 2.1
Q

T2g
2

A2g

Dq/B < 2.1

Q

T1g

Eg

Dq/B > 2.1

Q

(b) The luminescence behavior of some Oh Cr(III) complexes is tabulated below (energy in cm1 ).
Discuss the data with regard to the spectrochemical series and your plots in part a.
max (4 A2g 4 T2g ) max (4 A2g 2 Eg ) 0-0 (phos) max (uor)
3
CrCl6
13,060
14,480

11,600
CrF3
14,900
15,700

12,830
6
Cr(urea)3+
16,150
14,350
14,240
12,550
6
Cr(oxalate)3
20,800
?
13,420

3
Cr(NH3 )3+
17,500
14,350
14,390

6
Cr(phen)3+
21,550
15,300
15,120

3
Cr(CN)3
23,800
13,700
13,720

6
Cr(CH3 )3
26,600
12,470
12,430

6
Solution: As we read down the table we move through the spectrochemical series with increasing
Dq. As Dq increases, we move more into the strong-eld case depicted by the third potential
energy diagram. In this situation the 2 Eg surface drops in energy with increasing Dq as seen
by the second column of the table. Also, inner-system crossing becomes more favorable. The
rst potential energy diagram reveals an energy barrier moving from the 4 T2g to 2 Eg surface, but
for Dq/B > 2.1 the spin cross-over is downhill from the excited quartet state. When the 2 Eg
minima lies much lower than the 4 T2g minimua, the Boltzman factor will heavily favor intersystem
crossing into the 2 Eg state. This justies why phosphorescence is seen rather than uorescence
in the compounds with the largest values of Dq.
(c) Read the paper by Kenney, Clymire and Agnew (J. Am. Chem. Soc. 1995, 117, 1645-1646),
and summarize the interpretation of the spectrum reported in Figure 1. Draw an energy level
diagram as a function of pressure illustrating this situation.
Solution: In essence, Kenney et. al. report that they can take a weak eld Cr(III) coupound
and make it strong eld under high pressure since the ligands will be pushed closer to the Cr
center. In the strong eld limit the 2 Eg state is lower in energy than the 4 T2g excited state, so
phosphorescence replaces the usual weak-eld uorescence. Figure 1 in their paper displays the
emission spectrum as a function of pressure, demonstrating the gradual onset of a sharp phosphorescence peak along with the gradual loss of the vibrationally structured uorescence peak.
We can roughly say that Dq is proportional to pressure, allowing us to take the relative energy of
the 4 A2g , 4 T2g , and 2 Eg states from a normal Tanabe-Sugano diagram. There is some unknown
scaling factor between Dq and P , but the general situation is captured by the spin-crossover of
the excited state in the following diagram. (Obviously the plot is not accurate near P = 0)
60

50

E/B

40

T2g

Eg

A2g

30

20

10

8
10
12
Pressure (GPa)

19

14

16

18

20

10. Substitution reactions of low-spin Co(III) complexes generally proceed very slowly. Co(H2 O)3+
is a
6
striking exception. Taube and coworkers suggested that the high-spin term 5 T2g should be substitution
labile and thermally accessible. In order to ascertain whether this is reasonable, the energy gap between
the 1 A1g and 5 T2g must be determined (see the potential energy surfaces below).

Figure 7: Potential energy surfaces of Co(III)

(a) What is the problem with using straightforward ligand eld analysis to nd this energy dierence?
What is the vertical transition energy in terms of ligand eld parameters (EFC )?
Solution: The straightforward ligand eld analysis only pertains to vertical transitions, in which
the ligand-metal distances are held static. The sextet term has a larger equilibrium bond length,
so the minima of that potential energy surface is actually lower than EFC would suggest. It is the
energy of this minima that determines the Boltzmann factor. In Problem 7 I already solved for
this vertical transition energy.
EFC = 20Dq 18B 6C
(b) Experimentally observed splittings in the electronic origin of the 3 T1g term may be used to estimate
the position of the 5 T2g potential energy surface (Wilson and Solomon JACS 1980, 102, 40844095). The position of this surface may also be found using the following equation:


slope 5 T2g
slope 3 T1g

2
=

Sa1g (5 T2g )
Sa1g (3 T1g )

where slope refers to the slope of the curve on the Tanabe-Sugano diagram and the quantity S
is the Huang-Rhys factor for the normal coordinate of a1g symmetry in the indicated state.
S=

20

K(Q)2
2

The Tanabe-Sugano slope of the quintet term is twice that of the triplet term. It is then assumed
that the force constant for the 5 T2g totally symmetric vibration is K = K where K is the
ground state value and varies from 0 to 1. Locating the quintet surface now reduces to a
problem in analytical geometry.
1
E(1 A1g ) = KQ2
2
1
E(5 T2g = E0 + K (Q Q0 )2
2
EFC for the 1 A1g 5 T2g transition is just E(5 T2g ) evaluatied at Q = 0. Substituting into the expression for EFC the parameters Dq, B, and C, what is the separation of the minima of the ground
state and the rst quintet state potential energy surfaces? Let  = 357 cm1 . The reectance
spectrum of CsCo(SO4 )2 12H2 O yields Dq = 2080 cm1 , B = 513 cm1 , and C = 4250 cm1 .
Sa1g (3 T1g ) can be assumed to be 2.5 from Solomons work. Using this experimental data, calculate the energy gap E0 . Estimate the activation energy for the spin crossover process in kcal/mole.
Solution: The lowest energy strong-eld 3 T1g state has a t52g e1g conguration, so the slope with
respect to Dq is roughly 10. From part (a) we see that the slop for the 5 T2g state is 20. Hence
4=

Sa1g (5 T2g )
Sa1g (3 T1g )

We take the value of Sa1g (3 T1g ) from Solomon of 2.5, so we now have an estimate of Sa1g (5 T2g ).
The vertical transition energy is given by
1
E(5 T2g ) = E0 + K Q20 = 20Dq 18B 6C
2
E0 = 20Dq 18B 6C Sa1g (5 T2g )
E0 = 20Dq 18B 6C 4Sa1g (3 T1g )
Plugging in the given values yields

E0 = 3296 cm1

The activation energy is the energy at which the 1 A1g surface intersects the 5 T2g surface. For a
rough approximation at this energy we will set = 1 and solve for the intersection of the parabolic
surfaces. The intersection occurs at
EFC
Q= 
2K(EFC E0 )
and the intersection energy is
Eact =

2
EFC
= 3300 cm1 = 9.4kcal/mol
4(EFC E0 )

21

11. From analysis of the emission spectrum of K3 Co(CN)6 , Hipps and Crosby concluded that the maximum
of the 1 A1g 3 T1g transition in absorption to be at 20,300 cm1 . The emission peak at 14,000 cm1
was attributed to the 3 T1g 1 A1g transition.
(a) Is the predicted 20,300 cm1 band consistent with the expected reduction in the Racah parameter
C from the free ion value of 5120 cm1 ? Explain. If not, at approximately what energy would
you expect this transition?
For large Dq, the energy of the 3 T1g state is approximately (neglecting conguration interaction) given by
E(3 T1g ) = 14Dq + 15A 30B + 12C
and from Problem 7
E(1 T1g ) = 14Dq + 15A 30B + 14C = 32100 cm1
so the transition 1 A1g 3 T1g should have energy 32100 2C. With the assignment of Hipps
and Crosby this implies that C = 5900 cm1 . Hence the band position is not consistent with
the expected reduction in the Racah parameter C from its free ion value. I would expect C to
be reduced to about 4,000 cm1 , so the 1 A1g 3 T1g band should be around 32100 8000 =
24100 cm1 .
(b) IR studies indicate that the a1 (Co-C) stretch occurs at 414 cm1 . Discuss the following spectrum
in this context.

The ne structure on the spectra is spaced by 414 cm1 corresponding to increasing quanta of
the a1 vibrations.
(c) Discuss the signicance of the 1 A1g
ligand eld parameters Dq, B, and C.

T1g transition with regard to molecular geometry and

The excited triplet state adopts a diernt molecular geometry. We expect that the geometry
is still essentially octahedral, but the average bond lengths increase. At longer bond lengths the
overlap integrals are smaller, so Dq decreases. Also B and C tend to increase toward their freeion values. Essentially the excited electronic state acts like a distinct molecular species since its
molecular geometry changes. This means Dq, B, and C should be recalculated for the excited
state.
22

(d) The absorption spectrum of an excited state oers an interesting view of the energy level pattern
of a molecule. The hexacyanocobaltate ion gives rise to a structured d d transient absorption
spectrum obtained directly after laser excitation of the ground state system. The spectrum is
shown below. From Grith table A25, determine the energies of the relevant excited states.
Draw an energy level diagram illustrating these levels and the impact of conguration interaction
on their energies. Interpret the spectrum.

We are interested in the low-lying triplet states. We will take low-lying to mean all of the
triplet states arising from t52g e1g and t42g e2g congurations. From Table A29 of Griths we can
explicitly construct the electrostatic matrices including conguration interaction between the lowlying states:

T1g

15A 15B + 13C 8Dq

10B
=

0
3B 2

T2g

10B
15A 23B +11C 8Dq
2B 3
3B 2

15A 27B +11C 8Dq

=
2B 2
6B
3

0
2B 3
15A 25B +
11C 8Dq
B 6

2B 2
15A 23B +11C 8Dq
3B 2

3B 2

3B 2

B 6
15A 30B + 12C 18Dq

6B

3B 2
15A 22B + 11C 18Dq

Eg = 15A 25B + 11C 8Dq

A2g = 15A 16B + 14C 8Dq

The eigenvalues of these matrices give our energy levels, which are plotted using the values of
Dq = 3425 cm1 , B = 400 cm1 , C = 3050 cm1 .
23

x 10

3.5
3.45

3.4

3.5

3.35
Energy (cm1 )

Energy (cm1 )

4.5

x 10

3
2.5

1g

1.5

T2g

3.25
3.2

1g

Eg

3.15

3.1

2g

3.3

2g

0.5

Eg

A2g

3.05

3
No Conguration Interaction

With Conguration Interaction

No Conguration Interaction

(a)

(b)

With Conguration Interaction

Figure 8: Relevant excited triplet states with an without conguration interaction. Energies are given with
respect to the 3 T1g state, which is assumed to be the intermediate. Dq = 3425 cm1 , B = 400 cm1 , C =
3050 cm1

We note that the position of the bands does not seem to match the experiment by several thousand
wavenumbers. This is because the 3 T1g state has a dierent value of Dq, B, and C. The change
in Dq is most drastic. By setting Dq = 2475 cm1 the following plots were obtained, which have
much better agreement with the experiment.
4

x 10

2.65

x 10

2.6

3.5

2.55
2.5

2.5

Energy (cm1 )

Energy (cm1 )

2
3

1g

1.5

2.45
2.4
2.35
2.3

2.25

1g

2g

2g

A2g

0.5

2.2

2.15

2g

2.1
No Conguration Interaction

With Conguration Interaction

No Conguration Interaction

(a)

(b)

With Conguration Interaction

Figure 9: Relevant excited triplet states with an without conguration interaction. Energies are given with
respect to the 3 T1g state, which is assumed to be the intermediate. Dq = 2475 cm1 , B = 400 cm1 , C =
3050 cm1
Based on this calculation, the peak at 2.17 m1 is assigned to be both the 3 T1g 3 T1g and
3
T1g 3 T2g transition. The peak at 2.39 m1 is assigned to be the 3 T1g 3 Eg transition.
And the shoulder at 2.6 m1 is due to both the 3 T1g 3 T1g and 3 T1g 3 T2g transitions. My
assignment diers slightly from the assignment I found in a JACS paper by Viaene et. al. Viaene
clumped the higher energy 3 T1g 3 T1g transition in with the 3 Eg transition to account for the
middle peak.

24

12. The previous problem dealt with the structured emission spectrum of hexacyanocobaltate. Luminescence spectra are appropriate for investigation of vibrational progressions in electronic transitions,
since they can be measured with high sensitivity. The Frank-Condon principle may be used to evaluate the change in molecular geometry which accompanies an electronic transition. Such a vibronic
intensity analysis yields important information such as the excited-state geometry and excited-state
force constants. In this problem you will carry out a FC analysis of the hexacyanocobaltate emission
spectrum.
(a) Background material:
i. C.J. Ballhausen Molecular Electronic Structures of Transition Metal Complexes, sec. 4.7
ii. S.E. Schwartz J.Chem. Ed. 1973, 50, 608-610.
iii. G. Herzberg Spectra of Diatomic Molecules, chap. 4.
iv. M.A. Hitchman Trans. Met. Chem. 1985, 9, 1.
(b) The theory outlined below derives from work of Ansbacher (Z. Naturforsh. 1959, 14a, 889) and
Henderson and co-workers (J.Chem.Phys. 1964, 41, 580). The vibronic emission intensities are
given by:
64 4
2
4
2
cN E,
I, =
Re
| 
3 h4
Here E, is the energy of the electronic transition between vibrational states with the quantum
numbers and for the excited and ground vibrational states respectively. Re is the average
value of the electronic transition dipole moment, and the integrals are the Frank-Condon overlap
integrals hereafter called R, and N is the number of molecules in the initial state. In practice
the relative intensities can be related via the following equation.

4 
2
E0,n
R0,n
I0,n
=
I0,0
E0,0
R0,0
The frequency dependence for emission is given by:
E0,n = E0,0 nh0
where E0,0 is the energy of the electronic transition between the lowest vibrational states of the
excited and ground electronic states, and 0 is the eigenfrequency of the oscillator in the electronic
ground state. The most useful relations for the vibration overlap integrals are given by:
2
2
R0,0 =
e 2
1+

2DR0,n 2n( 2 1)R0,n1


R0,n+1 =
(1 + 2 ) 2(n + 1)
0
=
0

D = CS 0
D
=
1 + 2
When the displacement S of the minimum of the PE surface of the excited state along the
stretching coordinate S is expressed in angstroms, the vibrational energy in wavenumbers and the
masses of the ligands in amu, the constant C takes on the value 0.1722.
The distortions calculated from FC analysis are distortions in the normal coordinate whose vibrations comprise the progression in the spectrum. For the totally symmetric stretch in an octahedral
complex, the change in each metal ligand bond length is 16 S. S is normally determined by
calculating the vibronic band shape for dierent values of S and seeing which value most satisfactorily reproduces the observed spectrum.

25

(c) The energy of the vibronic peaks are given below:

E0,n (cm1 )
16,650
16,244
15,857
15,439
15,048
14,660
14,267
13,852
13,462
The origin for this progression is located at 17,020 cm1 . You may assume 0 = 0.65. Calculate
0
the vibronic intensity distribution and plot the intensities for the following values of S: (a)
0.05, (b) 0.3 and (c) 0.5
A. It may be useful to write a simple computer program to do these
calculations. From a comparison of these distributions and the known spectrum determine the
distortion of the metal ligand bonds in the excited state.
We aim to develop an expression for I0,n .

I0,n = I0,0

E0,n
E0,0

4 

R0,n
R0,0

2

I0,0 will be scaled to normalize the maximum intensity to 1.

E0,0 is the energy of the origin of the progression: 17,020 cm1 .
C = 0.1722
= 0.65

0.8

0.8

0.8

0.6
0.4
S = 0.05
0.2
0
0.8

Relative Intensity

1
Relative Intensity

Relative Intensity

0 can be obtained by averaging the energy gaps between adjacent energy peaks.
is the reduced mass, which is well approximated by the reduced mass between a Cobalt atom and
a carbon atom of the ligand. Using these values and the equations given in the problem a script
was written to generate plots for three values of S. Comparing these plots to the luminescence

0.6
0.4
S = 0.3
0.2

1.2
1.4
Energy (cm1 )

1.6

1.8
4

x 10

0
0.8

0.6
0.4
S = 0.5
0.2

1.2
1.4
Energy (cm1 )

1.6

1.8
4

x 10

0
0.8

1.2
1.4
Energy (cm1 )

1.6

1.8
4

x 10

spectrum from Problem 11 shows that S = 0.3 is the best t of the three options. Tuning the
value of S a little more shows that S = 0.25 actually produces a slightly better t. For the totally
A.
symmetric stretch, Q = 16 S, so Q 0.10
(d) What does this distortion imply with respect to excited state substitution reactions of these kinds
of complexes? You have t the spectrum using the symmetric stretching mode; what other mode
would you expect to be involved?

26

S = 0.25

Relative Intensity

0.8

0.6

0.4

0.2

0
0.9

1.1

1.2

1.3
1.4
Energy (cm1 )

1.5

1.6

1.7

1.8
4

x 10

This implies that the electronic excited state is very distorted, with a change in the ligand distance of 0.10
A. Hence the electronic excited state is expected to be more labile. The a1g vibration
does not alter the selection rules, so there is a progression of peaks due to dierent quanta of a1g
vibrations. The other involved mode is the mode that will allow the electronic transition from
A1g to T1g . From Problem 1 the octahedral vibrational modes are A1g Eg T2g 2T1g T2u .
The direct product of A1g , T1g , T1u , and the irrep of the vibration must contain A1g . This implies
that the allowing vibration is T1u .
(e) Recall the feature around 26,000 cm1 observed in the absorption spectrum of a thick crystal
of K3 Co(CN)6 (Problem 7). Estimate a value for the E0,0 of the emission band. How does this
change your result found in (c)? Comment on any changes in the quality of t.
If the absorption peak is at 26,000 cm1 rather than around 20,500 cm1 then E0,0 20,000
cm1 . This shift implies that the largest intensity emissions occur for even higher quanta of a1g
vibrations. This means S is even larger than anticipated from the calculation in part (c). The
quality of the t will be decreased since it will require essentially zero intenisty for the rst several
quanta of a1g vibration, then a sharp peak occuring nearly 15 vibrational quanta below E0,0 . The
slope of the peak intensity function cannot be very large for high number of quanta (ie there
cannot be a major dierence between I0,15 and I0,16 ). Hence it will not be possible to t the new
scenario to the luminescence spectra as closely.

27

13. This problem deals with the absorption spectrum of the square planar complex Ni(CN)2
4 .
(a) The solution spectrum is composed mainly of charge transfer transitions and has been interpreted
by Gray and Ballhausen (JACS 1963, 83, 260-264) using an MO scheme that predicts the same
ordering of terms as does the ligand eld theory for a strong tetragonal eld.

What happens to this ordering if a weak ligand eld treatment is used? Draw diagrams illustrating the eect of weak and strong tetragonal distortions on the energy levels and terms. The
dd transitions and proposed assignments for a single crystal of BaNi(CN)4 4H2 O are given below.
cm1
22,400
24,000
27,000


2
50
100

Assignment
A1g 1 A2g b2g b1g
1
A1g 1 B1g a1g b1g
1
A1g 1 Eg eg b1g
1

Solution: We rst consider the octahedral splitting then apply a weak tetragonal perturbation to
split the single electron t2g and eg levels. We know that in D4h , t2g eg t2g and eg a1g t1g .
Hence the ordering of the orbitals for a weak eld treatment is eg < b2g < a1g < b1g since the
energy of the derivatives of the t2g set never cross the energy of the derivatives of the eg set. This
is illustrated in Figure 5-1 in Ballhausen. I have reproduced a similar gure below.

b1g
b1g
eg
a1g

b2g

3d
a1g
b2g
t2g
eg
eg

Free Ion

Octahedral

Weak Tetragonal Strong Tetragonal

28

(b) Determine the symmetries of the normal vibrations in the Ni(CN)2

4 unit. Determine the selection
rules for d d transitions in the and polarizations.
Solution: Conveniently we note that we already found the symmetries of vibration for an analogous situation for Problem 8. We consider local x, y, and z coordinate systems on each of the C
and N atoms. The characters of interest are exactly twice he characters from Problem 8.
D4h
tot
rot
vib

E
24
3
21

2C4
0
1
-1

C2
0
-1
1

2C2
-4
-1
-3

2C2
0
-1
1

i
0
3
-3

2S4
0
1
-1

h
8
-1
9

2v
4
-1
5

2d
0
-1
1

Applying the great orthogonality theorem yields vib = 2A1g A2g 2B1g 2B2g Eg 2A2u
2B2u 4Eu .
We note that (x, y) transform as Eu while z transforms as A2u . The electronic states are all
g, so all transitions are Laporte forbidden. However, forbidden electronic transitions can couple
to the vibrational modes to become weakly allowed. This is summarized in the following tables.
Polarization (Eu ):
Ground State
1
A1g
1
A1g
1
A1g

Excited State
1
A2g
1
B1g
1
Eg

Vibration
Eu
Eu
A2u , B2u , Eu

Polarization (A2u ):
Ground State
1
A1g
1
A1g
1
A1g

Excited State
1
A2g
1
B1g
1
Eg

Vibration
Not Allowed (Requires A1u )
B2u
Eu

(c) The square planar anions in crystals of tetracyanonickelate salts typically stack to form a nearly
linear chain of nickel atoms. This allows for the determination of the absorption spectrum of the
crystal perpendicular and parallel to the stacking axis. The band at 23,000 cm1 is observed
only in the polarization. This indicates that the D4h selection rules deduced in part (b) may
not be appropriate. Read the paper by Ballhausen, Bjerrum, Dingle, Eriks, and Hare (Inorg.
Chem. 1965, 4, 514-518). Here cogent arguments are advanced to the eect that the D4h excited
states 1 B2g and 1 Eg are unstable with respect to distortion to the D2d states 1 B2 and 1 E1 in
D4h symmetry. The B2u vibration will transform a D4h molecule into a D2d molecule. [Note:
There seems to be a discrepancy. The Ballhausen paper says that the B1u vibration transforms
D4h into D2d . I will use Ballhausens symmetry. Further Note: I believe the discrepancy comes
from the fact that Ballhausens ligands lie o the x, y axes while Grays lie on the axes. This
interchanges b2 with b1 . Nevertheless, my method has been self consistent.] The 23,000 cm1
band must therefore terminate in a 1 B1g ? excited state. Fill in the ? and explain the
answer. Work out selection rules for the 1 A1g 1 B2 and 1 A1g 1 E transitions. Observe the
symmetry change. Finally draw qualitative PE curves for the 1 A1g , 1 A2g , 1 B2 , and 1 E terms on a
plot of energy vs. Q. Given the appearance of the 27,000 cm1 band is this assignment convincing?
Solution: We want the excited state to be allowed by parallel light when coupled to a B1u
vibration but not allowed by perpendicular light when coupled to the same B1u vibration. We

29

assume that the nal electronic state is of the form 1 B1g ? and the ground state is 1 A1g . For
parallel (z polarized) light we require
1

A1g A2u B1u 1 B1g ? = A1g

For perpendicular light we require

1

A1g Eu B1u 1 B1g ? = A1g

Equivalently these can be written as A2g ? = A1g and Eg ? = A1g . The second equation
implies that ? is a one-dimensional representation and the rst equation tells us that A2g = ? .
Hence the excited electronic state is 1 B2g in D4h symmetry but 1 B2 in D2d symmetry. From this
we have the fact that 1 A1g 1 B2 is allowed by parallel light by not allowed by perpendicular
light (assuming a coupling to the B1u vibration). The 1 A1g 1 E transition is allowed by
perpendicular light only. The qualitative potential energy surfaces are given below and are largely
inspired by Figure 6 of the Ballhausen paper. The square planar conguration corresponds to
Q = 0. As Q moves away from 0, the conguration becomes more tetrahedral, passing through
the D2d point group. I do not nd the assignment all that convincing based on the peak at 27,000

B2

A2g

A1g

cm1 . The peak appears in both the parallel and perpendicular spectra. In order to appear in
the parallel spectra, it requires that a Eg vibration be excited along with the B1u vibration that
takes the molecule from D4h to D2d symmetry. I would expect a broad peak from the vibrational
progression, but this is not seen as it was in the peak at 23,000 cm1 .
(d) From the band width at half max. and the band extinction coecient one nds an oscillator
strength of 5 x 106 for the transition at 22,400 cm1 . Based on the assignment given in part
(a), is this transition allowed by a magnetic dipole mechanism?
Solution: The magnetic dipole operator acts as Rx , Ry , and Rz , which transform as Eg and
A2g . We note that 1 A1g A2g 1 A2g = A1g , so the parallel magnetic dipole mechanism could
allow the transition.
(e) The band at 22,400 cm1 is only present in the spectrum of the barium salt and absent in spectra
of the strontium and calcium salts. It has been proposed that this feature may arise from a
30

spin-forbidden d d transition. Does this explanation seem plausible? The band at 22,400 cm1
is temperature dependent, red-shifting ( 300 cm1 ) and broadening with decreasing temperature
from 295 to 80 K. When crystals are doped with Pt(CN)2
4 anions, the band also red-shifts ( 500
cm1 ) and broadens. Below 90% nickel, the feature is no longer resolved. Given the structural
data summarized below, propose an alternative assignment for this transition. (Hint: consider
the report by Miskowski and co-workers (Inorg. Chem. 1994, 2799).)
Crystal
SrNi(CN)4 5H2 O
CaNi(CN)4 5H2 O
BaNi(CN)4 4H2 O

Ni Ni distance
3.64
A
3.39
A
3.36
A

C-Ni Ni-C Torsion

0
27
45

Solution: It seems conceivable that the band at 22,400 cm1 could be a spin-forbidden d d
transition since the heavy metals in Ba would lead to a greater degree of spin-orbit coupling.
However, one would expect these eects to also inuence the spectrum of the strontium salt,
at least slightly. It is more likely that the transition is due to metal-metal intervalence charge
transfer. In the barium salt, the stacks of (roughly) square planar molecules are rotated by 45
degrees from eachother. This allows the barium metals to pack closer together, allowing for more
bonding between the metal atoms.

31