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The electronic spectra of atoms

13.1 Spectroscopic terms

13.2 Terms of a d2 configuration

The electronic spectra of complexes

13.3 Ligand-field transitions

13.4 Charge-transfer bands

13.5 Selection rules and intensities

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

13.11 Binuclear complexes

Spectroscopic terms

The Russell Saunders Coupling Scheme

Quantum Numbers

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),

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.

ion is based on the results obtained by solving the Schrödinger Wave Equation for the H-

atom. 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, ....... , -(l-

2), -(l-1), -l.

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 + ½ or - ½.

Quantum Numbers

Principal Quantum Number - largely governs size of

n

orbital and its energy

Azimuthal/Orbital Quantum Number - largely

l

determines shape of orbital

ml Magnetic Quantum Number

Spin Quantum Number - either + ½ or - ½ for single

ms

electron

The ways in which the angular momenta associated with the orbital and spin motions in

many-electron-atoms can be combined together are many and varied. In spite of this

seeming complexity, the results are frequently readily determined for simple atom

systems and are used to characterise the electronic states of atoms.

• spin-spin coupling

• orbit-orbit coupling

• spin-orbit coupling

• and j - j coupling.

spin-spin coupling > orbit-orbit coupling > spin-orbit coupling.

This is found to give a good approximation for first row transition series where J

coupling is ignored, however for elements with atomic number greater than thirty, spin-

orbit coupling becomes more significant and the j-j coupling scheme is used.

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:

L 0 1 2 3 4 5

S P D F G H

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= + ½, 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.

Ground

Configuration Excited Terms

Term

d1,d9 2

D -

2 8 3

d ,d 3

F P, 1G,1D,1S

d3,d7 4

F 4

P, 2H, 2G, 2F, 2 x 2D, 2P

3

H, 3G, 2 x 3F, 3D, 2 x 3P, 1I, 2 x 1G, 1F, 2

d4,d6 5

D

x 1D, 2 x 1S

4

G, 4F, 4D, 4P, 2I, 2H, 2 x 2G, 2 x 2F, 3 x

d5 6

S 2

D, 2P, 2S

Hund's Rules

The Ground Terms are deduced by using Hund's Rules.

The two rules are:

1) The Ground Term will have the maximum multiplicity

2) If there is more than 1 Term with maximum multipicity, then the Ground Term will

have the largest value of L.

A simple graphical method for determining just the ground term alone for the free-ions

uses a "fill in the boxes" arrangement.

Ground

dn 2 1 0 -1 -2 L S

Term

d1 2 1/2 2

D

d2 3 1 3

F

3 4

d 3 3/2 F

4 5

d 2 2 D

5 6

d 0 5/2 S

6 5

d ¯ 2 2 D

d7 ¯ ¯ 3 3/2 4

F

8 3

d ¯ ¯ ¯ 3 1 F

9 2

d ¯ ¯ ¯ ¯ 2 1/2 D

To calculate S, simply sum the unpaired electrons using a value of ½ 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

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.

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.

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 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.

Saunders terms

in high spin octahedral crystal fields.

Russell-Saunders Crystal Field

Terms Components

S A1g

P T1g

D Eg , T2g

F A2g , T1g , T2g

G A1g , Eg , T1g , T2g

H Eg , 2 x T1g , T2g

I A1g , A2g , Eg , 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 Explanation

orbitals

Non-degenerate orbital; symmetric to

a

principal Cn

Non-degenerate orbital; unsymmetric to

b

principal Cn

e Doubly degenerate orbital

t Triply degenerate orbital

Symmetric with respect to center of

(subscript) g

inversion

Unsymmetric with respect to center of

(subscript) u

inversion

Symmetric with respect to C2 perp. to

(subscript) 1

principal Cn

Unsymmetric with respect to C2 perp. to

(subscript) 2

principal Cn

(superscript) ' Symmetric with respect to sh

(superscript) " Unsymmetric with respect to sh

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 non-

degenerate, 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 electronic spectra of complexes

The spectra of the aqua ions for some first row transition metal ions are shown below.

The observation of 2 or 3 peaks in the electronic spectra of d2, d3, d7 and d8 high spin

octahedral complexes requires further treatment involving electron-electron interactions.

Using the Russell-Saunders (LS) coupling scheme, these free ion configurations give rise

to F ground states which in octahedral and tetrahedral fields are split into terms

designated by the symbols A2(g), T2(g) and T1(g).

To derive the energies of these terms and the transition energies between them is beyond

the needs of introductory level courses and is not covered in general textbooks[10,11]. A

listing of some of them is given here as an Appendix. What is necessary is an

understanding of how to use the diagrams, created to display the energy levels, in the

interpretation of spectra.

A simplified Orgel diagram (not to scale) showing the terms arising from the splitting of

an F state is given below. The spin multiplicity and the g subscripts are dropped to make

the diagram more general for different configurations.

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.

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:

4

1. T2g ¬4A2g transition energy = D

4

2. T1g(F) ¬4A2g transition energy = 9/5 *D - C.I.

4

3. T1g(P) ¬4A2g 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).

Cr3+ in emerald 16260 23700 37740 1.46 0.686 20.4 13

work

work

work

3

1. T2g ¬3A2g transition energy = D

3

2. T1g(F) ¬3A2g transition energy = 9/5 *D - C.I.

3

3. T1g(P) ¬3A2g 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).

[Ni(H2O)6]2+ 8500 13800 25300 1.62 0.616 11.6 13

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).

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.

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.

3

T1g(P) ¬ 3T1g transition energy = 3/5 *D + 15B' + 2 * C.I.

The transition energies of these terms are clearly different and it is often necessary to

calculate (or estimate) values of B,D and C.I. for both arrangements and then evaluate the

answers to see which fits better.

The difference between the 3A2g and the 3T2g (F) lines should give D. In this case D is

equal to either:

25200 - 17400 = 7800 cm-1

or 34500 - 17400 = 17100 cm-1.

Given that we expect D to be greater than 15000 cm-1 then we must interpret the second

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.

The first obvious difference to the Orgel diagrams shown in general textbooks is that

Tanabe-Sugano diagrams are calculated such that the ground term lies on the X-axis,

which is given in units of D/B. The second is that spin-forbidden terms are shown and

third that low-spin complexes can be interpreted as well, since for the d4 - d7 diagrams a

vertical line is drawn separating the high and low spin terms.

The procedure used to interpret the spectra of complexes using Tanabe-Sugano diagrams

is to find the ratio of the energies of the second to first absorption peak and from this

locate the position along the X-axis from which D/B can be determined. Having found

this value, then tracing a vertical line up the diagram will give the values (in E/B units) of

all spin-allowed and spin-forbidden transitions.

N.B. Another approach has been to use the inverse of this ratio, ie of the first to second

transition and so both values are recorded in the Tables.

As an example, using the observed peaks found for [Cr(NH3)6]3+ in Table 1 above then,

from the JAVA applet described below, D/B' is found at 32.6. The E/B' for the first

transition is given as 32.6 from which B' can be calculated as 661 cm-1. The third peak

can then be predicted to occur at 69.64 * 661 = 46030 cm-1 or 217 nm (well in the UV

region and probably hidden by charge transfer or solvent bands).

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

T2g¬3T1g and the second and third to 3T1g (P) ¬3T1g (blue line) and 3A2g¬3T1g (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.

[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.

UV spectra from a) [Cr(en)3]3+; b) [Cr(ox)3 ]3-; c) [CrF6]3-. υ 1 = ∆o. (roughly)

Selection rules:

1) Laporte: change of parity (g -> u or u -> g) required for an allowed transition. E.g., all

d-d transitions of centrosymmetric (octahedral) complexes are Laporte forbidden thus

weak.

2) Spin rule: an allowed transition must not involve a change in the total spin. Thus, no

transitions are spin-allowed in a d5 high spin complex.

Range of molar absorptivities

ε [L mol-1 cm-1

type of transition examples

]

Spin and Laporte forbidden 10-3 - 1 [Mn(H2O)6]2+

Spin allowed, Laporte

1 - 10 [Ni(H2O)6]2+

forbidden

Spin allowed, Laporte

10 - 102 [PdCl4]2-

forbidden

Spin allowed, Laporte six-coordinated complexes of low

102 - 103

forbidden symmetry

Spin and Laporte allowed 102 - 103 metal-ligand CT bands

2 4

Spin and Laporte allowed 10 - 10 acentric complexes

3 6

Spin and Laporte allowed 10 - 10 CT bands

Correlation diagram for d2 in octahedral ligand field

Tanabe-Sugano

2

diagram for d in octahedral ligand field; Spin-allowed

transitions

[M(H2O)6]n+

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.

L(t1) -> M(e) at 17700 cm-1 (565 nm)

L(t1) -> M(t2*) at 29500 cm-1 (340 nm)

L(t2) -> M(e) at 30300 cm-1 (330 nm)

L(t2) -> M(t2*) at 44400 cm-1 (225 nm)

Remember, visible light includes wavelengths between ca. 400 and 750 nm, i.e.

frequencies between 25000 and 13000 cm-1. This explains the deep purple color of MnO4-

( complementary to green).

Further examples: CrO42-: orange; HgI2 , red; BiI3, orange-red; PbI2: yellow.

Example for MLCT: filled M orbitals and empty low lying L orbitals needed, e.g. π

antibonding orbitals like in CO and pyridine.

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