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Note that CFT can only predict the splitting pattern of the d-orbitals.
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
S= 0 1 3/2 2 5/2
2S + 1 1 2 3 4 5 6
Examples:
For a d1 configuration:
S= +, hence (2S+1) = 2 ; L=2
and the ground term is written as 2D doublet dee
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
A simple graphical method for determining just the ground term alone
for the free-ions uses a "fill in the boxes" arrangement.
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
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.
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
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.
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
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.
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.
For M2+ complexes, expect = 7500 - 12500 cm-1 or = 800 - 1350 nm.
For M3+ complexes, expect = 14000 - 25000 cm-1 or = 400 - 720 nm.
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.