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Spectroscopic terms
The Russell Saunders Coupling Scheme
Quantum Numbers
Electrons in an atom reside in shells characterised by a particular value of n, the Principal
Quantum Number. Within each shell an electron can occupy an orbital which is further
characterised by an Orbital Quantum Number, l, where l can take all values in the range:
l = 0, 1, 2, 3, ... , (n-1),
traditionally termed s, p, d, f, etc. orbitals.
Each orbital has a characteristic shape reflecting the motion of the electron in that
particular orbital, this motion being characterised by an angular momentum that reflects
the angular velocity of the electron moving in its orbital.
A quantum mechanics approach to determining the energy of electrons in an element or
ion is based on the results obtained by solving the Schrdinger Wave Equation for the Hatom. The various solutions for the different energy states are characterised by the three
quantum numbers, n, l and ml.
ml is a subset of l, where the allowable values are: ml = l, l-1, l-2, ..... 1, 0, -1, ....... , -(l2), -(l-1), -l.
There are thus (2l +1) values of ml for each l value,
i.e. one s orbital (l = 0), three p orbitals (l = 1), five d orbitals (l = 2), etc.
There is a fourth quantum number, ms, that identifies the orientation of the spin of one
electron relative to those of other electrons in the system. A single electron in free space
has a fundamental property associated with it called spin, arising from the spinning of an
asymmetrical charge distribution about its own axis. Like an electron moving in its
orbital around a nucleus, the electron spinning about its axis has associated with its
motion a well defined angular momentum. The value of ms is either + or - .
In summary then, each electron in an orbital is characterised by four quantum numbers:
Quantum Numbers
n
spin-spin coupling
orbit-orbit coupling
spin-orbit coupling
Spin-Spin coupling
S - the resultant spin quantum number for a system of electrons. The overall spin S arises
from adding the individual ms together and is as a result of coupling of spin quantum
numbers for the separate electrons.
Orbit-Orbit coupling
L - the total orbital angular momentum quantum number defines the energy state for a
system of electrons. These states or term letters are represented as follows:
Spin-Orbit coupling
Coupling occurs between the resultant spin and orbital momenta of an electron which
gives rise to J the total angular momentum quantum number. Multiplicity occurs when
several levels are close together and is given by the formula (2S+1).
The Russell Saunders term symbol that results from these considerations is given by:
(2S+1)
L
As an example, for a d1 configuration:
S= + , hence (2S+1) = 2
L=2
and the Ground Term is written as 2D
The Russell Saunders term symbols for the other free ion configurations are given in the
Table below.
Configuration
d1,d9
Excited Terms
d ,d
P, 1G,1D,1S
d3,d7
d4,d6
d5
dn
-1
-2
Ground
Term
d1
1/2
d2
3/2
5/2
3/2
d7
2
1/2 D
To calculate S, simply sum the unpaired electrons using a value of for each.
To calculate L, use the labels for each column to determine the value of L for that box,
then add all the individual box values together.
For a d7 configuration, then:
in the +2 box are 2 electrons, so L for that box is 2*2= 4
in the +1 box are 2 electrons, so L for that box is 1*2= 2
in the 0 box is 1 electron, L is 0
in the -1 box is 1 electron, L is -1*1= -1
in the -2 box is 1 electron, L is -2*1= -2
Total value of L is therefore +4 +2 +0 -1 -2 or L=3.
Note that for 5 electrons with 1 electron in each box then the total value of L is 0.
This is why L for a d1 configuration is the same as for a d6.
The other thing to note is the idea of the "hole" approach.
A d1 configuration can be treated as similar to a d9 configuration. In the first case there is
1 electron and in the latter there is an absence of an electron ie a hole.
The overall result shown in the Table above is that:
4 configurations (d1, d4, d6, d9) give rise to D ground terms,
4 configurations (d2, d3, d7, d8) give rise to F ground terms
and the d5 configuration gives an S ground term.
The Crystal Field Splitting of Russell-Saunders terms
The effect of a crystal field on the different orbitals (s, p, d, etc.) will result in splitting
into subsets of different energies, depending on whether they are in an octahedral or
tetrahedral environment. The magnitude of the d orbital splitting is generally represented
as a fraction of Doct or 10Dq.
The ground term energies for free ions are also affected by the influence of a crystal field
and an analogy is made between orbitals and ground terms that are related due to the
angular parts of their electron distribution. The effect of a crystal field on different
orbitals in an octahedral field environment will cause the d orbitals to split to give t2g and
eg subsets and the D ground term states into T2g and Eg, (where upper case is used to
denote states and lower case orbitals). f orbitals are split to give subsets known as t1g, t2g
and a2g. By analogy, the F ground term when split by a crystal field will give states
known as T1g, T2g, and A2g.
Note that it is important to recognise that the F ground term here refers to states arising
from d orbitals and not f orbitals and depending on whether it is in an octahedral or
tetrahedral environment the lowest term can be either A2g or T1g.
Crystal Field
Components
A1g
T1g
Eg , T2g
Eg , 2 x T1g , T2g
Note that, for simplicity, spin multiplicities are not included in the table since they remain
the same for each term.
The table above shows that the Mulliken symmetry labels, developed for atomic and
molecular orbitals, have been applied to these states but for this purpose they are written
in CAPITAL LETTERS.
Mulliken Symbols
Mulliken Symbol
for atomic and molecular
orbitals
Explanation
(subscript) g
(subscript) u
(subscript) 1
(subscript) 2
(superscript) '
(superscript) "
For splitting in a tetrahedral crystal field the components are similar, except that the
symmetry label g (gerade) is absent.
The ground term for first-row transition metal ions is either D, F or S which in high spin
octahedral fields gives rise to A, E or T states. This means that the states are either nondegenerate, doubly degenerate or triply degenerate.
We are now ready to consider how spectra can be interpreted in terms of energy
transitions between these various levels.
*13.2 Terms of a d2 configuration
The lines showing the A2 and T2 terms are linear and depend solely on D. The lines for
the two T1 terms are curved to obey the non-crossing rule and as a result introduce a
configuration interaction in the transition energy equations.
The left-hand side is applicable to d3 , d8 octahedral complexes and d7 tetrahedral
complexes. The right-hand side is applicable to d2 , d7 octahedral complexes.
Looking at the d3 octahedral case first, 3 peaks can be predicted which would correspond
to the following transitions:
1.
2.
3.
T2g 4A2g
T1g(F) 4A2g
4
T1g(P) 4A2g
4
transition energy = D
transition energy = 9/5 *D - C.I.
transition energy = 6/5 *D + 15B' + C.I.
Here C.I. represents the configuration interaction which is generally either taken to be
small enough to be ignored or taken as a constant for each complex.
In the laboratory component of the course we measure the absorption spectra of some
typical chromium(III) complexes and calculate the spectrochemical splitting factor, D.
This corresponds to the energy found from the first transition above and as shown in
Table 1 is generally between 15,000 cm-1 (for weak field complexes) and 27,000 cm-1
(for strong field complexes).
Table 1. Peak positions for some octahedral Cr(III) complexes (in cm-1).
Complex
n1
n2
n3
n2/n1
n1/n2
D/B
Ref
Cr3+ in emerald
16260
23700
37740
1.46
0.686
20.4
13
K2NaCrF6
16050
23260
35460
1.45
0.690
21.4
13
[Cr(H2O)6]3+
17000
24000
37500
1.41
0.708
24.5
This
work
Chrome alum
17400
24500
37800
1.36
0.710
29.2
[Cr(C2O4)3]3-
17544
23866
1.37
0.735
28.0
This
work
[Cr(NCS)6]3-
17800
23800
1.34
0.748
31.1
[Cr(acac)3]
17860
23800
1.33
0.752
31.5
This
work
[Cr(NH3)6]3+
21550
28500
1.32
0.756
32.6
[Cr(en)3]3+
21600
28500
1.32
0.758
33.0
[Cr(CN)6]3-
26700
32200
1.21
0.829
52.4
T2g 3A2g
3
T1g(F) 3A2g
3
T1g(P) 3A2g
transition energy = D
transition energy = 9/5 *D - C.I.
transition energy = 6/5 *D + 15B' + C.I.
where C.I. again is the configuration interaction and as before the first transition
corresponds exactly to D.
For M(II) ions the size of D is much less than for M(III) ions (around 2/3) and typical
values for Ni(II) are 6500 to 13000 cm-1 as shown in Table 2.
Table 2. Peak positions for some octahedral Ni(II) complexes (in cm-1).
Complex
n1
n2
n3
n2/n1
n1/n2
D/B
Ref
NiBr2
6800
11800
20600
1.74
0.576
13
[Ni(H2O)6]2+
8500
13800
25300
1.62
0.616
11.6
13
[Ni(gly)3]-
10100
16600
27600
1.64
0.608
10.6
13
[Ni(NH3)6]2+
10750
17500
28200
1.63
0.614
11.2
13
[Ni(en)3]2+
11200
18350
29000
1.64
0.610
10.6
[Ni(bipy)3]2+
12650
19200
1.52
0.659
17
For d2 octahedral complexes, few examples have been published. One such is V3+ doped
in Al2O3 where the vanadium ion is generally regarded as octahedral, Table 3.
Table 3. Peak positions for an octahedral V(III) complex (in cm-1).
Complex
n1
n2
n3
n2/n1
n1/n2
D/B
Ref
V3+ in Al2O3
17400
25200
34500
1.45
0.690
30.8
13
Interpretation of the spectrum highlights the difficulty of using the right-hand side of the
Orgel diagram above for many d2 cases where none of the transitions correspond exactly
to D and often only 2 of the 3 transitions are clearly observed.
The first transition can be unambiguously assigned as:
3
T2g 3T1g
transition energy = 4/5 *D + C.I.
But, depending on the size of the ligand field (D) the second transition may be due to:
3
A2g 3T1g
transition energy = 9/5 *D + C.I.
for a weak field or
T1g(P) 3T1g
transition energy = 3/5 *D + 15B' + 2 * C.I.
transition as to the 3T2g(P) and the third to 3A2g. Further evaluation of the expressions
then gives C.I. as 3720 cm-1 and B' as 567 cm-1.
Solving the equations like this for the three unknowns can ONLY be done if the three
transitions are observed. When only two transitions are observed, a series of
equations[14] have been determined that can be used to calculate both B and D. This
approach still requires some evaluation of the numbers to ensure a valid fit. For this
reason, Tanabe-Sugano diagrams become a better method for interpreting spectra of d2
octahedral complexes.
For the V(III) example treated previously using an Orgel diagram, the value of D/B'
determined from the appropriate JAVA applet is around 30.8.
Following the vertical line upwards leads to the assignment of the first transition to
3
T2g3T1g and the second and third to 3T1g (P) 3T1g (blue line) and 3A2g3T1g (green line)
respectively.
The average value of B' calculated from the three Y-intercepts is 598 cm-1 hence D equals
18420 cm-1, significantly larger than the 17100 cm-1 calculated above and shows the sort
of variation expected from these methods.
It is important to remember that the width of many of these peaks is often 1-2000 cm-1 so
as long as it is possible to assign peaks unambiguously, the techniques are valuable.
Charge-transfer bands
Selection rules and intensities
Electronic Absorption Spectroscopy
The d-d transitions in complex ions correspond to absorptions which are often, though
not always, the cause for their colour. The position of absorption peaks in the spectra
allow the direct measurement of . This is particularly straightforward for ions with a d1
or d10 configurations.
Some complexes, usually very intensely coloured, owe their colour to charge-transfer
transitions which involve the excitation of an electron from a molecular orbital largely
centered on the metal to one largely centered on the ligands or vice versa. Such
transitions often result in a big dipole change for the molecule which is a factor which is
associated with a highly probable transition and hence an intense colour.
Selection Rules for d-d Transitions and Colour Intensity (Section 13.5)
The Laporte Rule. In a molecule or ion possessing a centre of symmetry, transitions are
not allowed between orbitals of the same type, for example d to d. The geometries
affected by this rule include octahedral and square-planar depending on the ligands and
isomers involved. The rule never applies to tetrahedral complexes.
In cases where the rule applies, the colours of the complexes are usually relatively pale.
The reason transitions are observed at all is because the symmetry centre is transiently
destroyed by vibrations of the molecules or ions.
As examples, consider [Cu(H2O)6]2+ which is a rather pale blue colour vs
[Cu(NH3)4]2+ which is an intense dark blue.
Spin Allowed - Spin Forbidden Transitions which would require an electron to change
its spin are strongly forbidden. Consider the case of the high spin d5 complex
[Mn(H2O)6]2+. This complex is sometimes very pale pink due to the presence of very
small amounts of impurities.
Finally, bear in mind that allowed and Laporte forbidden transitions can occur outside the
visible region of the spectrum if the crystal field splitting is very large. This can happen
with strong field ligands such as CN or CO.
13.6 Luminescence
13.7 Spectra of f-block complexes
13.8 Circular dichroism
13.9 Electron paramagnetic resonance
*Bonding and spectra of M-M bonded compounds
13.10 The ML5 fragment
UV spectra
As we noticed before, a lot of complexes give rise to colorful solutions because of d-d
transitions. Keep in mind that we see the complementary color when visible light of any
wavelength is absorbed. In the Figure on the left, complementary colors are situated on
the opposite sides.
[L mol-1 cm-1
]
examples
10-3 - 1
[Mn(H2O)6]2+
1 - 10
[Ni(H2O)6]2+
10 - 102
[PdCl4]2-
102 - 103
102 - 103
metal-ligand CT bands
acentric complexes
CT bands
10 - 10
10 - 10
Tanabe-Sugano
Spin-allowed
[M(H2O)6]n+
Charge transfer spectra
Charge transfer: Electron transfer from M to L or from L to M, i.e. an electron moves
from a M-based orbital to a L-based orbital or vice versa [ligand-to-metal charge transfer,
LMCT; metal-to-ligand charge transfer, MLCT ).
Since this resembles an internal redox process, the charge transfer will depend on
electron affinities and ionization energies.
How to favor LMCT: take M with high ionization energy, i.e. low lying empty d orbitals,
and L with low electron affinity, i.e. filled orbitals at high energies. Examples are M =
MnVII, PtIV ; L = Se2-, I-. If the d orbitals lie lower than the filled L orbitals, then a
complete internal redox reaction takes place, like in [Co(H2O)6]3+ and FeI 3.
Example for MLCT: filled M orbitals and empty low lying L orbitals needed, e.g.
antibonding orbitals like in CO and pyridine.