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The following figure shows the UV-Visible absorption spectra for aqueous solutions of first-row
transition metal complexes with the formula [M(H2O)6 ]x+ (x = 2 or 3).
Note that in the preceding absorption spectra, the y-axes show molar absorptivity ( with units of
dm3 mol-1 cm-1) which is calculated from the measured absorbance (A) by the equation
log(I o /I) = A = cl {Io = incident light intensity; I = emerging light intensity; c = concentration
(mol dm-3), l = pathlength through the test solution (cm)}.
From the UV-Visible absorption spectra on the previous page, it can be seen that certain complexes
have relatively simple spectra (e.g. d1, HS d4, HS d6 and d9 complexes), while others are far more
complex.
First, let us look at the simplest case; the aqueous Ti3+ ion (d1 ) which displays only one band in the
UV-Visible absorption spectrum. Considering the splitting of the d-orbitals in an octahedral
environment, this band can be assigned to the transition eg1 t2g1 as shown below:
eg
hv
o = hc/max
t2g
eg
hv
t2g
Since the t2g and eg* sets of orbitals are degenerate, we might expect to see only one absorption in the
spectrum. However, there are clearly two bands in the spectrum of [V(H 2O)6] 3+ on page 1. Consider
the relative orientations of orbitals involved in the electronically excited states of V 3+ :
3
Interelectronic repulsion makes excited state configurations such as those shown below
non-degenerate. As a consequence, more than one absorption band is observed and o cannot be
obtained directly from the position of the maximum in the spectrum.
dz2
dxy
dx2-y2
dxz
dz2
dyz
dxy
dx2-y2
dxz
dyz
absorption
spectra
of
transition
metal
4
A What different combinations of ml and ms possible for two d-electrons, and how may the
electronic quantum numbers (ml and ms) be combined to give the atomic quantum numbers ML
and MS which describe atomic microstates?
Remember that an electron may be described using four quantum numbers (n = principal q.n.; l =
orbital angular momentum q.n.; ml = magnetic q.n.; ms = spin q.n. ).
For a gas-phase d1 ion, the lone d-electron can take values of ml = +2, +1, 0, -1, -2 and ms = +1/2,
-1/2, which gives a total of 10 possible arrangements of ml and ms. In the absence of an electric or
magnetic field, these 10 arrangements are degenerate (all of the same energy).
For a gas-phase d2 ion, one electron can in principle have ten different arrangements of ml and ms as
shown below , while the other can have nine different combinations (Pauli Exclusion Principle),
giving a total of 90 possible combinations . However, since the two d-electrons are indistinguishable
particles, the number of possible states is reduced to 45.
The two d-electrons are not independent of each other and their orbital angular momenta
(characterized by ml values) and spin angular momenta (characterized by ms values) interact in a
manner called Russell-Saunders coupling. These interactions produce states called microstates that
can be described by the new quantum numbers M L and M S :
First electron:
ml = +2 and ms = +1/2
Second electron:
ml = 0 and ms = -1/2
Notation: 2+0 -
5
We have seen that for a d configuration, there are 10 possible microstates, and for a d ion, there are
1
45 microstates. In general, for a subshell (of certain l) with n electrons, the equation below can be
used to calculate the total number of states:
[2(2l+1)]!
n![2(2l+1) n]!
M S = +1
M L = +2
M L = +1
2 2
2+ 1+
2+ 0+
2+ -1+
1+ 0+
ML = 0
2+ -2+
1+ -1+
M L = -1
-2+ 1+
-1+ 0+
M L = -2
M L = -3
M L = -4
M S = -1
+ -
M L = +4
M L = +3
MS = 0
-2+ 0+
-2 -1
2+ 12 - 1+
2+ 02 - 0+
1+ 1 2+ -1 2- -1+
1+ 0 1- 0+
2+ -2 2- -2+
1+ -1 1- -1+
0+ 0 -2+ 1 -2 - 1+
-1+ 0 -1 - 0+
2- 1-
2- 0-
= 1G
= 3F
2- -11- 0-
= 1D
= 3P
= 1S
2- -21- -1-
-2 - 1-1 - 0-
-2+ 0 -2 - 0+
-1+ -1-
-2 - 0-
-2- -1-
For a collection of microstates (we will learn how to group microstates into terms with the same
energy next), S and L are the largest positive values of M L and M S w ithin the collection. For example,
for the group of microstates; {2+ 2- }, {2+ 1 -}, {2+ 0- }, {2+ -1 -}, {2+ -2- }, {-2+ 1- }, {-2+ 0- }, {-2+ -1-},
{-2+ -2-}, L = 4 and S = 0. While the value of S is represented by a number, the value of L is
represented by a letter (see below). Therefore, for this collection of microstates, the term symbol
(defined by (2S+1)L , where 2S+1 is calle d the spin multiplicity) is 1G.
L = 0 S term
L = 1 P term
L = 2 D term
L = 3 F term
L = 4 G term
L = 5 H term
L = 6 I term
* Now we consider the remaining microstates. Choose the one with the largest M L (and the largest
M S if there are several microstates with the same maximum M L) that has not yet been assigned: {2+
1+} in this case, which has M L = 3 and M S = 1. This must be the first microstate in the term 3F, which
will have (2L+1)(2S+1) = (2x3+1)(2x1+1) = 7x3 = 21 microstates. After assigning all of these 21
microstates, we are left with 15 microstates. Following the same method we can identify the other
terms of this configuration: 1D, 3P and 1S.
The same procedure can be used to determine the terms for different d-electron configurations, and
the resulting terms for each configuration are shown below:
d1
d2
d3
d4
d5
d6
d7
d8
d9
D
S, 1D, 1G, 3P , 3F
D, 4P , 4F, 2P , 2D, 2F , 2G, 2H
D, 1S, 1D, 3P , 3F, 3P, 3D, 3F , 3G, 3H, 2S, 1D, 1F, 1G, 1I
D, 4P , 4F, 2P , 2D, 2F , 2G, 2H, 2S, 2D, 2F, 2G, 2I, 4D, 4G, 6S
D, 1S, 1D, 3P , 3F, 3P, 3D, 3F , 3G, 3H, 2S, 1D, 1F, 1G, 1I
D, 4P , 4F, 2P , 2D, 2F , 2G, 2H
S, 1D, 1G, 3P , 3F
D
8
ml
Configuration
2
1
ML
-1
-2
?
?
?
?
?
?
?
?
3
?
?
?
3
?
?
2
?
Ground
Term
2
?
MS
1/2
3/2
5/2
D
F
F
D
S
??
d7
??
??
3/2
D
F
??
??
??
d9
??
??
??
??
1/2
Note that these simple rules can only be used to identify the ground state term. In order to find the
energy of the higher energy terms, Schrdingers equation must be solved, which involves the
evaluation of many 2-electron integrals. Racah worked out all of the integrals for a d2
configuration, and found that they can be classified into three sets called A, B and C. Even better, he
found that the energy of all terms can be written as simple combinations of these integrals. The
values of A, B and C can be computed, but are more frequently matched to spectroscopic results, and
are thus used as parameters. Of the three parameters, A is not meaningful when dealing with
differences in energy between terms rather than actual energies. In addition, it is found that in many
cases C 4B. This permits fairly simple interpretation of spectra using only parameter B, which is
called the principal Racah parameter.
Using either Crystal Field Theory or Ligand Field Theory, confinement of a metal ion in an
octahedral environment results in a splitting of the energy into the t2g and eg* sets. For the
monoelectronic d1 system, there is only one possible electronic transition e g1 t2g1 (see below). The
2
D term corresponds to a d2 atom or ion in the gas phase, while the two possible electronic
configurations in an octahedral environment, t2g and eg * result in two terms 2Eg* and 2T 2g. Notice the
distinction of electronic configuration and spectroscopic terms using a different letter case. The
difference in energy between 2Eg* and 2T 2g is also called o, and as ligand field strength increases, o
increases.
2006 - Dr. Paul G. Hayes University of Lethbridge
9
2E
g
0.6 o
2T
2g
Ion in the
gas phase
Increasing Ligand
Field Strength
0.4 o
Oh
The figure shown above is called a correlation diagram, and indicates the relationship between the
free ion terms for a gas phase ion and an ion in an octahedra l environment (Oh). Correlation diagrams
depict the energy of the O h terms in relation to the parent free ion term.
For other dn configurations (n > 1), the reduction in symmetry also results in splitting of the terms.
This splitting is formally obtained using group theory, but for our purposes, it is enough to examine
the end result shown in the table below:
A1g
T1g
Eg + T2g
A2g + T1g + T 2g
A1g + Eg + T1g + T 2g
10
The correlation diagram below shows the splitting of the important triplet terms ( F and P) for the d2
3
configuration:
Field strengths for
actual complexes
Infinitely high
field strength
3
A2g
eg2
o
3P
T1g
3T
2g
t2g1eg1
approx
o
3F
o
3T
1g
Ion in the
gas phase
Increasing Ligand
Field Strength
t2g2
Oh
The free d2 ion is shown on the left hand side of the diagram, while the right hand side of the
diagram shows the energy levels in an infinitely strong ligand field (not one that could be found in a
real complex). At this strong field limit, the effects of the ligands is so strong that it completely
overrides Russell-Saunders coupling, and we are left with the familiar electronic configurations of
t2g2 , t 2g1eg1 and eg2. At this strong field limit, o can easily be marked on the diagram. In actual
compounds, the situation is intermediate between these two extremes. However, by looking at these
extremes, it can be seen that in the central region of the diagram, o is represented by 3T2g 3T1g
and 3A 2g 3T2g transitions. Note: the former of these transitions cannot be used reliably to find Do
because 3T 1g does not vary linearly with o (the line is curved see later).
G - Tanabe-Sugano diagrams.
A Tanabe-Sugano diagram is a special type of correlation diagram that is particularly useful for the
interpretation of electronic spectra for transition metal complexes. In a Tanabe-Sugano diagram, the
ground state term is set as the base line and all other energies are referenced to this ground state. The
energy and o are presented as multiples of the principal Racah parameter B, and energies are
calculated using a value of C (~ 4) which is reported in the diagram.
11
It is fortunate that we do not need to carry out detailed analysis for all cases. The Tanabe -Sugano
diagrams have been worked out for most dn configurations with common geometries (e.g. octahedral
and tetrahedral). Tanabe-Sugano diagrams for octahedral complexes are shown below.
12
n
13
Tetrahedral Complexes
The same octahedral Tanabe-Sugano diagrams can be used for tetrahedral complexes. However, for a
dn tetrahedral complex, the d(10-n) Tanabe-Sugano diagram must be used (i.e. for d8 T d, use the d2 O h
T-S diagram). For more details, see Miessler and Tarr, Inorganic Chemistry, 3rd Edition, pg 406.
2006 - Dr. Paul G. Hayes University of Lethbridge
14
Some important general observations from the Tanabe -Sugano diagrams are:
(1) Some lines are curved. This arises because whenever two states of the same symmetry (same
term symbol) are close in energy, they can be combined to yield one state of lower energy and
another of higher energy. In a Tanabe-Sugano diagram, this makes it appear that some lines bend
away from each other to avoid crossing. As a result, this phenomenon is referred to as the noncrossing rule. Note that transitions involving these curved lines must be avoided when determining
o from Tanabe-Sugano diagrams.
(2) For some configurations, there is an abrupt change of slope and the ground state term also
changes. This happens when there is a transition from a High-Spin to a Low -Spin state.
Spin Selection Rule Transitions between different spin multiplicities are forbidden. For example,
transitions between 4A2 and 4T1 states are spin-allowed, but between 4A 2 and 2A2 are spin-forbidden.
Laporte (Parity) Selection Rule Transitions between states of the same parity (symmetry with
respect to inversion) are forbidden. For example, transitions between d-orbitals are forbidden (these
are g g transitions) but transitions between d and p orbitals are allowed (g u).
These rules would seem to rule out many of the electronic transitions for metal complexes (see
Tanabe-Sugano diagrams). However, many transition metal complexes are famous for their bright
colours; a consequence of various mechanisms by which the above rules can be relaxed. The most
important relaxation mechanisms are:
15
* Vibronic Coupling (molecular vibrations ) temporarily changes molecular symmetry, and can result
in temporary loss of the centre of symmetry in an octahedral complex. This provides a way to relax
the Laporte selection rule. As a consequence, d-d transitions often have extinction coefficients ( ) of
10 to 100 dm 3 mol-1 cm-1 which is responsible for the bright colours of many transition metal
complexes.
* Tetrahedral C omplexes absorb more strongly than octahedral complexes. Metal-ligand -bonding
in transition metal complexes of T d symmetry, and the lack of a centre of symmetry makes
transitions between d-orbitals more allowed (relaxa tion of the Laporte selection rule ). As a result,
extinction coefficients of around = 500 dm3 mol-1 cm-1 are common. As a qualitative example,
[Ni(H 2O)6]2+ is pale green while [Ni(PPh3)4 ]2+ is deep blue.
* Spin-Orbit Coupling can provide a mechanism for relaxation of the spin selection rule . Such
absorption bands for first-row transition metal complexes are generally weak, with typical extinction
coefficients of around = 1 dm3 mol-1 cm-1. For example, octahedral Mn2+ complexes (d5) cannot
undergo any spin-allowed transitions from the 6A1 ground state, so are extremely pale coloured. By
contrast, Spin-Orbit coupling can be more important for 2nd and 3rd row transition metal complexes.
The molar absorptivity (, extinction coefficient) is a good indicator of the type of electronic
transition:
(dm3 mol-1 cm-1)
Example
<1
Mn 2+ (aq)
d-d Laporte-forbidden
10-100
Most 3d Oh complexes
~ 500
Td complexes
~ 10,000
Organic chromophores
Type of transition
Spin-forbidden
Note: while it is important to have an idea of what the different terms on a Tanabe-Sugano diagram
represent, it is most important to be able to use Tanabe-Sugano diagrams and molar absorptivity to
interpret and understand the electronic spectra of transition metal complexes (including finding o or
t for a complex).
See annotations to TS diagrams made in lecture for finding o spectroscopically.
16
CHARGE TRANSFER ABSORPTIONS
[Cr(NH3)6]3+ : there is an intense absorption in the UV region of the spectrum. This type of intense
absorption ( ~ 104 dm3 cm-1 mol-1) can be seen more clearly in [CrCl(NH3)5] 2+:
[Cr(NH3)6]3+
[CrCl(NH3)5] 2+
Note: The lowest energy dd transitio n in [CrCl(NH3)5]2+ is significantly lower in energy than that
of [Cr(NH3)6] 3+ due to a lower o (Cl- is lower in the spectrochemical series than NH3).
Note: For [CrCl(NH3)5] 2+, there are shoulders on the dd transitions due to reduced symme try
(C4v instead of Oh).
Both peaks are examples of LMCT (Ligand to Metal Charge Transfer), which involves the transfer
of electrons from molecular orbitals that are primarily ligand based to orbitals that are primarily
metal based.
17
Other examples of complexes with prominent LMCT absorptions are shown below (relative energies
of the LMCT absorptions are also shown using < and >). These are all d0 complexes, so cannot
undergo dd transitions:
3d easier
to reduce
3d
MnO 4-
4d
<
TcO4-
CrO 42-
MoO 42-
<
^
VO43-
5d
<
NbO43-
M7+
^
<
^
<
ReO4-
WO42-
higher
oxidation state
metal is easier
to reduce
M6+
^
<
TaO 43-
M5+
In complexes containing ligands which have low-lying empty *-orbitals, MLCT (Metal to Ligand
Charge Transfer) can be observed. This is often found for diimine type ligands (bipyridine,
phenanthrolene) as well as a variety of other soft ligands such as S2C2R2x-, S2CNR2-, CO, CN- and
SCN-. See molecular orbital dia gram above.
Examples of molecules which show strong MLCT bands are [M(bipy) 3]2+ (M = Fe or Ru),
[W(CO)4(phen)] and [Fe(CO)3(bipy)].
[Cr(CO)6] shows both LMCT and MLCT absorptions.
Both MLCT and LMCT results in a dramatic redistribution of electron density between the metal and
the ligands (hence the name charge transfer). This redistribution of electron density results in
differences in the solvation for the ground state and excited state molecules. As a result, the energy
of charge transfer bands is highly dependent on solvent (SOLVATOCHROMISM).
----------------------------------------------------------------
18
LUMINESCENCE
A complex is luminescent if it emits radiation after it has been electronically excited by the
absorption of radiation. Luminescence competes with non-radiative decay by thermal dissipation of
energy (heat loss to the surroundings).
Luminescence can be divided into two categories:
(1) Fluorescence Radiative decay from an excited state with the same multiplicity as the ground
state. This process is fast (nanoseconds).
(2) Phosphorescence
Radiative decay from an excited state with different multiplicity from the
ground state. This process is spin-forbidden, so is usually slow
(microseconds to seconds). The mechanism of phosphorescence involves
intersystem crossing (the non-radiative conversion of the initial excited
state into another excited state of different multiplicity). This second
excited state acts as an energy reservoir because radiative decay to the
ground state is spin forbidden.
Ruby is an important example of a phosphorescent compound. Ruby absorbs green and violet light
so appears red. Red phosphorescence helps to enhance the red colour and lustre of ruby (see below).
Ruby = Al2O3 with partial replacement of Al3+ by Cr3+ - the Cr 3+ ions are dilute and are surrounded
by an octahedral arrangement of oxide ligands.
Molecular examples of phosphorescent complexes include [Cr(bipy) 3]3+ and [Ru(bipy) 3]3+.
The first laser (1960) was based on ruby.
----------------------------------------------------------------
19
LASERS
A synthetic ruby rod is irradiated using a powerful xenon lamp (see below).
The long lifetime of the metastable 2Eg level (~ 4 ms) means that with suitably intense
irradiation, more than half of the chromium ions can be excited to the 2Eg level at one time. This
is called a population inversion.
Decay of these excited state chromium ions results in a photon at 694 nm.
The ruby rod is housed between 2 mirrors (one fully reflecting and one only partially reflecting).
Therefore, if the 694 nm photon is emitted in the correct direction, it bounces back and forward
between the two mirrors. When it encounters another excited state Cr 3+ ion, it can cause decay
by stimulated emission. This stimulated emission results in production of a photon that relative
to the photon that stimulated the emission, is at exactly the same wavelength, is in phase and is
travelling in the same direction (i.e. the light produced is monochromatic, coherent and
collimated).
The two photons now move back and forwards between the two mirrors in the resonant cavity,
which results in more stimulated emission. As a result, the intensity of the beam of photons
increases with each pass through the cavity until it reaches a ste ady state (see figure below).
Remember that one of the mirrors at the end of the resonant cavity is only partially reflecting. A
portion of the coherent, collimated and monochromatic light is therefore able to escape through
this output mirror, resulting in a laser beam (see below).
Other common types of laser include: other solid state lasers (e.g. Yttrium Aluminium Garnet
(YAG) doped with Nd3+, Ho3+ or Er3+; YAG = Y 3Al5O12 ), dye lasers (e.g. a dilute solution of
rhodamine or fluorescein ), gas lasers (e.g. He/Ne, Ar, Ar/Kr, CO2) and semiconductor lasers
(e.g. InGa/AlP). Solid state and dye lasers are generally excited using optical pumping. Gas
lasers and semiconductor lasers generally use electrical pumping.