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magnitude of o This depends on the ligands bonded to the metal.

some ligands induce large o high energy absorption

others induce small o low energy absorption

Hence different complexes of the same metal in the same oxidation state

may exhibit different colours have different absorption spectra.

to higher energy d orbital.

Note that CFT can only predict the splitting pattern of the d-orbitals.

Types of transition

these are often extremely intense

are generally found in the UV region but they may have a

tail into the visible spectrum.

are predominantly metal d orbitals

the separation is characterised by the strength of o.

can occur in both the UV and visible region.

transitions usually have small to medium intensities.

Electronic spectra of TM complexes

A single transition t2g2eg1

t2g3 has resulted into two

bands in the spectrum of the

d3 complex [Cr(NH3)6]3+ due

to electron-electron

repulsions.

spectra:

Spectrum of the d 3 complex [Cr(NH ) ]3+.

Understand how to obtain 3 6

o from electronic

absorption spectrum of a The key point is that the presence of e-e

TM complex with more repulsions within d orbitals mean that

than one d electron when e- absorption frequencies

o because e-e

e repulsions are important. repulsions result in multiple absorptions.

Revision on Quantum Numbers (QN)

l = Azimuthal/Orbital QN shape of orbital 0, 1, 2, 3..n-1

ml = Magnetic QN

ms = Spin QN for a single electron

L 0 1 2 3

orbital s p d f

ml 1 3 5 7

i.e. for the 1 s orbital (l = 0), 3 p orbitals (l = 1), 5 d orbitals (l = 2), etc.

Microstates

The different ways in which electrons can occupy the orbitals specified

in configuration are called microstates.

For example, one microstate of a 2p2 configuration is (1+ , 1-), this

notation signifies that both the electrons occupy an orbital ml = +1

but do so with opposite spins.

+ indicates ms = + and indicates ms = -.

Another microstate of the same configuration is (-1+ , 0+).

In this microstate, both the electrons have ms = + but one occupies

the 2p orbital with ml = -1 and the other occupies the orbital ml = 0.

The microstates of a given configuration will have the same energy

only if electron-electron repulsions are negligible.

If we group together the microstates that have the same energy taking

into account e-e repulsions , we obtain energy levels called TERMS.

Russell-Saunders (R-S) coupling

The interactions that can occur are of three types:

spin-spin coupling S

orbit-orbit coupling L

spin-orbit coupling J

Russell-Saunders (or L - S) coupling

j - j coupling.

It follows that we can identify the terms of light atoms and put them in

order of energy by sorting the microstates according to their total spin

quantum number S and then according to their total orbital angular

momentum quantum number L.

This process called Russel-Saunders coupling.

Russell- Saunders Coupling

the total orbital angular momentum of an atomic term is denoted by

the equivalent upper case letter:

L = 0 1 2 3 4.

S P D F G.(omitting J)

The total spin is normally reported as the value of 2S + 1, which is

called the multiplicity of the term:

S= 0 1 3/2 2 5/2

2S + 1 1 2 3 4 5 6

Russell Saunders term symbol

The multiplicity is written as a left superscript representing the value of L

and the entire label of a term is called a term symbol.

Examples:

For a d1 configuration:

S= +, hence (2S+1) = 2 ; L=2

and the ground term is written as 2D doublet dee

S= both +, hence (2S+1) = 3; or paired hence (2S+1) = 1 ; L=0+1=1

and the terms arising from this are 3P (triplet pee) or 1P (singlet pee)

For a p1d1 configuration: terms arising are 3F (triplet eff) or 1F (singlet eff)

TRY THIS AT HOME

Mulliken symbols for atomic and molecular orbitals

Symbol Meaning

a or A Non-degenerate orbital; symmetric to principal Cn

b or B Non-degenerate orbital; unsymmetric to principal Cn

e or E Doubly degenerate orbital or state

t or T Triply degenerate orbital or state

(subscript) g Symmetric with respect to centre of inversion

(subscript) u Unsymmetric with respect to centre of inversion

(subscript) 1 Symmetric with respect to C2 perp. to principal Cn

(subscript) 2 Unsymmetric with respect to C2 perp. to principal Cn

except that the symmetry label g (gerade) is absent.

Energies of the terms- Hund's Rules

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

1) The Ground Term will have the maximum multiplicity.

Ground Term will have the largest value of L.

Thus for a d2 the rules predict 3F < 3P < 1G < 1D < 1S

A simple graphical method for determining just the ground term alone

for the free-ions uses a "fill in the boxes" arrangement.

d9 has 1electron less than d10 i.e. a hole.

d-orbital ground terms

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.

in the +2 box are 2 electrons, so L for that box is 2 x 2= 4

in the +1 box are 2 electrons, so L for that box is 1 x 2= 2

in the 0 box is 1 electron, L is 0

in the -1 box is 1 electron, L is -1 x 1= -1

in the -2 box is 1 electron, L is -2 x 1= -2

Total value of L is +4 +2 +0 -1 -2 = 3 F term.

for each.

4

For maximum multiplicity S = 2s+1 = 2[3()] + 1 = 4 F

Also possible is S = 2s+1 = 2[1()] + 1 = 2 2P

Note that for 5 electrons with 1 electron in each box then the total

value of L is 0 L for a d1 configuration = L for a d9.

d-orbital ground terms

dn 2 1 0 -1 -2 L S Ground Term

d1 2 1/2 2D

d2 3 1 3F

d3 3 3/2 4F

d4 2 2 5D

d5 0 5/2 6S

d6 2 2 5D

d7 3 3/2 4F

d8 3 1 3F

d9 2 1/2 2D

4 configurations (d1, d4, d6, d9) give rise to D ground terms,

4 configurations (d2, d3, d7, d8) give rise to F ground terms

d5 configuration gives an S ground term.

Terms for 3dn free ion configurations

The Russell Saunders term symbols for the other free ion

configurations are given in the Table below.

# of # of

Configu Ground

micro energy Excited Terms

ration Term

states levels

d1,d9 10 1 2D -

d2,d8 45 5 3F 3P, 1G,1D,1S

d4,d6 210 16 5D

1I, 2 x 1G, 1F, 2 x 1D, 2 x 1S

d5 252 16 6S

2G, 2 x 2F, 3 x 2D, 2P, 2S

Q.

What is the ground term of the configurations:

(a) 3d5 of Mn2+ and

(b) 3d3 of Cr3+?

Answer:

If done correctly you should come up with (a) = 6S (a sextet ess term) and

(b) = 4F (a quartet eff term).

S = 2 2S + 1 2 x 2 + 1 = 6 A sextet

L = 2 + 1 + 0 -1 -2 = 0 6S term

(b) S = 1 2S + 1 2 x 1 + 1 = 4 A quartet

L = 2 + 1 + 0= 3 4F term

The ligand field splitting of TM complex ground terms

Thus far our discussion refer only to free atoms, we will now take it a

step further to the domain of TM complex ions.

influence of a ligand field.

The effect of a ligand field d orbitals split into t2g and eg subsets.

By analogy the D ground term states split into T2g and Eg.

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.

Correlating the splitting of spectroscopic terms in Oh ligand field

S 1 A1g

P 3 T1g

D 5 Eg , T2g

F 7 A2g , T1g , T2g

G 9 A1g , Eg , T1g , T2g

Note: The ground term for first-row transition metal ions is either:

D, F or S which in high spin Oh A, E or T states.

Due to d-d transitions the spectrum shows two central bands with

intermediate intensities.

How do we account for two bands in a single electron transition?

Spectroscopic terms

The terms of an octahedral complex are labelled by the symmetry species

of the overall orbital state; a superscript prefix shows the multiplicity of

the term:

The ground term of the d 3 Cr3+ discussed above is 4F which gives rise

to 4A2g , 4T1g , 4T2g in the octahedral crystal field.

The two eg t2g transitions of the excited state are thus labeled:

4T 4A

2g and T2g A2g.

4 4

1g

atomic term symbols discussed earlier on.

WITH ORBITALS ALL TERM SYMBOLS ABOVE ARISE

FROM d-ORBITALS. WE ARE MERELY USING ANALOGY

WITH ORBITALS FOR CONSISTENCY.

For ALL octahedral complexes, except high spin d5, simple CFT would

predict that only 1 band should appear in the electronic spectrum and

that the energy of this band should correspond to the absorption of

energy equivalent to .

observed for those ions with D free ion ground terms i.e., d1, d9 as well

as d4, d6.

and d8 high spin octahedral complexes requires further treatment

involving electron-electron interactions.

configurations give rise to F free ion ground states which in octahedral

and tetrahedral fields are split into terms designated by the symbols

A2g, T2g and T1g.

Ligand field transitions

t2g3 absorption near 25 000 cm-1 excitation t2g2eg1 t2g3.

There are 2 eg t2g transitions possible:

The dz2 dxy transition, promotes The dz2 dzx transition merely

an electron from the xy-plane into relocates an electron that is

the already electron-rich z-direction already largely concentrated

(the axis is electron-rich because along the z-axis.

both dyz and dzx are occupied

large e-e repulsion). Here there is no e-e repulsion.

Selection rules for electronic spectra of TM complexes.

levels of transition metal complexes are:

The first rule states that allowed transitions must involve the promotion

of electrons without a change in their spin.

The second rule states that if the molecule has a centre of symmetry,

transitions within a given set of p or d orbitals (i.e. those which only

involve a redistribution of electrons within a given subshell) are

forbidden.

Selection rules for electronic spectra of TM complexes.

vibrations where the molecule is asymmetric

Absorption of light at that moment is then possible.

transitions are no longer purely d-d.

Electronic Spectra

Expected Values:

For M2+ complexes, expect = 7500 - 12500 cm-1 or = 800 - 1350 nm.

For M3+ complexes, expect = 14000 - 25000 cm-1 or = 400 - 720 nm.

around 50-100 times smaller than for tetrahedral complexes.

an octahedral complex, expect < 10 m2mol-1.

Electronic Spectra

Example: The complex [(Co(NH3)6]+3 absorbs light with a wavelength

of 437 nm. What is the splitting energy ?

be equal to the light energy absorbed.

E = hc/

h = 6.626 x 10-34 Js ;

c = 3.00 x 108 m/s and

= 437 nm = 4.37 x 10-7 m.

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