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Chem 310 Fall 1999

Solutions to Problem Set 4


1) How many microstates are possible for the following configurations:

(i) the ground configuration of Ti2+ ?


(ii) the ground configuration of Co3+?

Remember the meaning of nCr = (n!)/[r!(n-r)!] for the number of possible combinations. In
the case of Ti2+ we have a d2 configuration, and the number of microstates is (10!)/[(8!)( 2!)]
= 45. Co3+ is a d6 ion but is easier to visualize it in terms of the number of holes rather
than the number of electrons, i.e., a d6 is equivalent to a d4, and the possible combinations
are (10!)/[(6!)(4!)] = 210.
2) Identify the ground state term symbols for Fe2+, Ni2+, Ti2+, Mn2+.

OK, here we are using are knowledge of Hund’s Rules, i.e.,

1. The ground state will have the highest multiplicity (be high spin).
2. For states of the same multiplicity, that with the higher L value will ne lower in
energy.
3. For given L and S values, that with the lowest J value [J = *L+S*, ... , *L-S*] is the
lowest energy. For shells that are greater than half-filled, this latter ordering is
reversed.

The idea then is to set out an array of the possible ml values, slap the electrons into the boxes
so as to generate the maximum ML (= sum of the ml’s) with the maximum Ms (i.e., hold the
electrons spin up). This creates a microstate which is the “wing tip” of the state that fulfils
rules 1 and 2. For the record the total degeneracy of the state (number of microstates with
the same energy) is (2S+1)(2L+1). Let’s do it...

Fe2+ = d6
ml 2 1 0 -1 -2

This is a greater than half-filled shell, we could treat it as a d4 system. Either way, the ML
value is 2 and the MS value also is 2. This is the “wing tip” microstate of a L = 2, S = 2

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state, i.e., a 5D state, for which the multiplicity is 5 × 5 = 25. In other words the
microstate identified is one of 25 twin siblings (energetically speaking). The possible J
states, which arise from spin orbit coupling, are J = 4, 3,2,1,0. Because this is a greater
than half-filled shell, the J = 4 state is the lowest in energy.
ml 2 1 0 -1 -2
Ni2+ = d8

This again is a greater than half-filled shell, we could treat it as a d2 system. Either way,
the ML value is 3 and the MS value also is 1. This is the “wing tip” microstate of a L =
3, S = 1 state, i.e., a 3F state, for which the multiplicity is 3 × 7 = 21. In other words
the microstate identified above is one 21 twin siblings (energetically speaking). The possible
J states, which arise from spin orbit coupling, are J = 4, 3,2. Because this is a greater than
half-filled shell, the J = 4 state is the lowest in energy.
ml 2 1 0 -1 -2
Ti2+ = d2

Been there, done it. This is the same as the d8 ion above. The ML value is 3 and the MS
value is 1. This is the “wing tip” microstate of a L = 3, S = 1 state, i.e., a 3F state, for
which the multiplicity is 3 × 7 = 21. The possible J states, are J = 4, 3,2. Because this
is a less than half-filled shell, the J = 2 state is the lowest in energy.
ml 2 1 0 -1 -2
Mn2+ = d5

This is the classic high spin log jam. The ML value is 0 and the MS value also is 5/2. This
is the “wing tip” microstate of a L = 0, S = 5/2 state, i.e., a 6S state, for which the
multiplicity is 6 × 1 = 6. As for the possible J states, which arise from spin orbit coupling,
there is only one, with J = 5/2.

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3) Identify the ground term symbols from each of the following sets of terms.

(a) 1G, 3F, 3P, 1P


(b) 3H, P, 5D, 1I, 1G
(c) 6S, 4G, 4P, 2I

Specify the spin and orbital angular momenta (L and S) for the ground state, and also the possible total
angular momentum values J. Specify lowest spin orbit component (assuming a > half-filled band), and also
the degeneracy (number of microstates for the lowest spin orbit state).

Answer this question by inspection of the Term Symbol. Remember what the symbol is
telling you. The prefix tells you the multiplicity (the total spin angular momentum S), the
main letter the total orbital angular momentum L. The state with the lowest L and lowest
S is the ground state. For a greater then half filled configuration the largest J component is
the lowest in energy. Hence:

(a) 3
F ground state, with J = 4, 3, 2. J = 4 is the lowest state. The degeneracy of any
J-state is 2J+1. In this case, the degeneracy is 9.

(b) 5
D ground state, with J = 4, 3, 2, 1, 0. J = 4 is the lowest state. The degeneracy
of any J-state is 2J+1. In this case, the degeneracy is 9.

(c) 6
S ground state, with J = 5/2. J = 5/2 is the ground spin orbit state with a
degeneracy of 6 microstates.

4) Close analysis of the electronic spectrum of Ni(H2O)62+reveals absorption maxima at 8600, 13,500 and
25,300 cm-1. There are also two extremely weak bands at 15,400 and 18,400 cm-1 . Consult the appropriate
Tanabe Sugano diagram and assign all these transitions. Estimate 10Dq and B.

If you look at the Tanabe Sugano diagram for a d8 ion in the Appendix 5 of Schriver you’ll
see the expected features - a 3A ground state and three spin allowed 3T excited states. All
these we built in class. You’ll also see 1A and 1E terms trucking across almost parallel to
the ground state, i.e., not dependent on 10Dq. The two weak bands correspond to these spin
forbidden transitions, which amount to spin flips of electrons within the eg set. As you would
expect, the energies if these transitions should be largely independent of the value of 10Dq.

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Ground spin allowed spin forbidden
State

3 3 1 1
3
A T ,3T T A E

As for calculating 10Dq, remember that for a d8 ion the lowest frequency band gives 10Dq
directly. Thus 10Dq = 8600 cm-1. You can get at B by numerical or graphical methods.
The ratio of <2/<1 is 13.5/8.6, or about 1.57. Tracking on the TS diagram for the x-
coordinate corresponding to this ratio in the two low energy 3T states yields a value of
10Dq/B near 10. Hence, B is about 860 cm-1 (compared to 1003 cm-1 for gas phase Ni2+).

5) Consult your class notes for the relationships between the excitation frequencies and the 10Dq and B values
of a d3 ion. Use Jorgensen's f, g, h, k constants to predict the spin allowed transitions in the UV-visible
spectrum of Cr(NH3)63+. The ruby laser contains Cr3+ ions in a Oh environment surrounded by oxide ions.
Explain the excitation and emission processes on which the laser action hinges. Is the value of 10 Dq
important?

The following data applies:

Cr3+ g = 17.0, h = 0.21 NH3 f = 1.25, k = 1.4

B for Cr3+ free ion = 1030 cm-1

Thus 10Dq = (g × f) × 103 cm-1 = 1.25 ×17.0 × 103 = 21,250 cm-1

and B = Bfree ion (1- k.h) = 1030 (1 - 0.294) = 727 cm-1

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You could calculate the three frequencies using the formulas in the class notes or, more
simply, read the frequencies off the Tanabe Sugano diagram. I took the latter route.

10Dq/B = 29.2

<1 = 28B = 20 ×103 cm-1 (at best my eyes are good to 2 sig. figs)

<1 = 47B = 34 ×103 cm-1

<3 = 61B = 24 ×103 cm-1


4
2 T1g intersystem
4
T1g Eg crossing
4
T 2g 2
4
T2g Eg
luminescence
(with stokes shift)

4 phosphorescence
A2 g 4
A2 g
Cr3+ (weak field) Cr3+ (medium field)

The critical feature of the electronic structure of ruby crystals is the proximity of the doublet
and quartet manifolds. The ligand field is such that they are right beside one another (about
10Dq/B = 20). A spin-orbit driven intersystem crossing is most efficient under these
circumstances, so that one can really build up a population inversion in the 2E state.

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6) Salts of Mn(II) in aqueous solution are almost colourless. This we have ascribed to the fact that in a high
spin d5 ion all transitions are spin-forbidden. That doesn't mean they don't occur, it just means that they will
be very weak. What causes the apparent slight breakdown of the spin selection rule? The spectrum of a
typical Mn(II) complex is provided in class notes. You will note that the lines are much sharper than those
observed for most other complexes. Why is this so?

The spin selection rules breaks down as spin-orbit coupling


causes an intersystem crossing - a change in multiplicity.
Typically, these effects are much more important in the heavier
metals and lanthanides. The spectrum of Mn2+ exhibits a series
of weak but sharp lines which arise because of spin turnovers,
in which electrons are flipped inside the t2g and eg sets rather
than excited between them. These transitions result in very little
structural change (they are not t2g to eg) during the excitation, so
that the so-called Franck-Condon envelope (remember CHEM 6
S
129?) is very narrow.

7) Solutions of [Cr(H2O)6]2+ ions are pale blue-green, but the chromate ion [CrO4]- is a very intense yellow.
Characterize the origins of the expected transitions and explain the relative intensities.

In Cr2+ we are dealing with Laporte forbidden d-d transitions, while in the chromate ion the
transitions are ligand to metal charge transfer bands, which are very intense.
CrO4- (LMCT)
Cr2+ (d to d) F*
B*

Metal
d-orbitals

5
E 5
T B
ligand
orbitals

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8) Shown below is a Tanabe-Sugano diagram.
2
90
3
80 (i) For what octahedral first row M2+ ion is this figure
applicable?
70
4 (ii) What is the physical significance of the dashed
60 vertical line?
E/B
1 (iii) Indicate the term symbols of the states designated
50 by the numbers 1 to 5.
(iv) Determine (using Jorgensen’s constants) whether
40
the M(NH3)62+complex will be high or low spin.
30 5

20

10

4 10 20 30
F
10Dq/B

This is a Sherlock Holmes type problem. A 2+ metal ion with a 4F ground state. That has
to be d3 or a d7. It has to be the latter, as there is a huge spin cross-over line (the dashed
vertical line) in the middle. So that makes it Co2+. Cranking the handle as we have done
before the excited states for such a system (if high spin) in Oh symmetry are:
Low Spin
Ground State
High Spin Excited States
Ground State

4 4
T T ,4T 4
A
2
E

The excited states 2,3, and 4 above correspond to those shown at left. State 5 is the high spin
ground state, i.e., 4T, while state 1 is the low spin 2E ground state.

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Finally the synthesis of the electronic spectrum via Jorgensen parameters follows directly
from problem 5. With Co2+ and ammonia as a ligand,

g = 9.3, k = 0.24, f =1.25, h = 1.4, Bfree ion = 970 cm-1

This gives 10Dq = (g × f )× 103 cm-1 = 11,625 cm-1 and B = 970 (1 - 0.336) = 644 cm-1
Hence 10Dq/B = 18.0, i.e., an x-coordinate to the high spin side of the spin cross over line.

9) The complex [Cr(CN)6]3- has absorption bands at 264, 310 and 378 nm. Estimate )0 and B using a Tanabe
Sugano diagram. First, decide how to assign the observed transitions, noting that the ligand has empty B
orbitals. The complex also luminesces at 725 nm. Is this fluorescence or phosphorescence? (Hint. Check
the full Tanabe Sugano diagram in Schriver for spin forbidden transitions.)

What you have to do here is haul out (again!) Appendix 5 of Schriver, in order to examine
the Tanabe Sugano diagram for a d3 metal ion. The lowest energy transition gives 10Dq
directly (26,460 cm-1), and from the ratio of the first and second bands (1.22) we can lock
in approximately where on the x-coordinate the
system lies. I found it easier and quicker to estimate 4T g
1
B from Jorgensen parameters k and h, and I got 597
cm-1, a low value in keeping with cyanide’s good 4
ability to “cloud expand”. T2 g

One can then estimate 10Dq/B to be near 44 B, intersystem


i.e., way out on the strong field side of the Tanabe crossing
Sugano diagram, as expected. The state diagram 2
will thus look like this: Eg

The luminescence we are looking at is at very much


lower energy than the excitations, and results from
an ISC (intersystem crossing) from the quartet to phosphorescence
doublet manifolds. This is phosphorescence. 4
A2 g

Cr3+ (very strong field)

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10) The intense purple colour of the permanganate ion consists of two transitions at 18,500 and 32,200 cm-1.
Explain how you could estimate 10Dq for MnO4- from this information.

Mn(VII) is d0 complex so we are clearly dealing with LMCT bands from the oxygen lone
pairs to the empty t2g and eg sets. One can get a handle on 10Dq nonetheless simply by
measuring the difference in the two lowest energy transitions, as shown below. For this
system 10Dq = 32,000 - 18,500 = 13,500 cm-1.

F*
B*
M L

h< Metal
d-orbitals

B
ligand
orbitals

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