Unidad 2 - Parte 1 - Teoría Del Campo Cristalino, Espectroscopia Electrónica

Universidad del Valle
Inorganic Chemistry II
Prof. Renso Visbal Acevedo Departamento Química
email: renso.visbal@correounivalle.edu.co
Electronic Spectroscopy and Magnetism
Transition Metal Complexes
Mixed valence [CoFe] complexes and

cyanide-bridged discrete molecules
HOT TOPIC exhibit photoinduced switching
between antiferromagnetic and
ferromagnetic phases.
When the complex was irradiated (λ =

808 nm) with the temperature set at 5
K, a rapid increase of χmT values was
observed after ten hours of
irradiation.
[Co(II)((R)-pabn)] [Fe(III)(tp)(CN)3](BF4)•MeOH•2H2O
Taken from Nature Chemistry, 2012, 4, 921-926
Light-Induced Spin Change by Photodissociable External

Ligands: A New Principle for Magnetic Switching of Molecules
HOT TOPIC
Published in: J. Am. Chem. Soc. 2011, 133,

16243-16250.
Copyright © 2011 American Chemical Society
Crystal Field Theory of
Crystal Field Theory
Molecular Orbital Theory is the most complete theory use for the
understanding of the vast majority of chemical and physical properties
observed in simple and complex molecules. So, Why Crystal Field Theory
is so important?
The complexes behave as if the bonding between the central metal ion
and the surrounding ligands is purely electrostatic.
z
+
M
x y
Octahedral Complexes A metal s orbital in an octahedral complex
A set of metal p orbitals in an octahedral crystal field
The dxy, dyz and dzx metal orbitals in an octahedral crystal field
The dx2-y2 and dz2 orbitals in an octahedral crystal field
Although they look very different, the fact that they can be mixed by an axis
relabelling shows that they are a degenerate pair
T1u T2u
In an octahedral crystal field the f orbitals of a metal atom

split into two sets which are triply degenerate and one orbital
which is singly degenerate
A2u
In an octahedral crystal field the f orbitals of a metal atom

split into two sets which are triply degenerate and one orbital
which is singly degenerate
The orientation of the five d orbitals with respect to the

ligands of an octahedral complex: the degenerate (a) eg and
(b) t2g orbitals
The mean energy remains

unchanged relative to the
energy of the d orbitals in a
spherically symmetrical
environment
The energies of the d orbitals in an octahedral crystal field

d x2-y2, d z2 (eg)
3Δ
5
-2 Δ
5
dxy, dyz, dzx (t2g)
The d orbital splitting in an octahedral

crystal field
Δ value for metals of the first raw:

M+: 10.000 cm-1
M2+: 5.000-15.000 cm-1
M3+: 10.000-30.000 cm-1
This value is up to twice for second The optical absorption

or third raw complex spectrum of [Ti(OH2)6]3+
Ligand-field splitting parameters ∆O of ML6 complexes
Values are in cm1-; entries in parentheses are for low-spin complexes

Spectrochemical Series
I- < Br- < S2- < SCN- < Cl- < NO2- < N3- < F- < OH- < C2O42- < O2- < H2O <
NCS- < CH3CN < py < NH3 < en < bpy < phen < NO2- PPh3 < CN- < CO
Mn2+ < Ni2+ < Co2+ < Fe2+ <V2+ <Fe3+ < Cr3+ < V3+ < Co3+ < Mn4+ < RhIII <
PdIV < IrIII < PtIV
Ligand-field stabilization energies
To predict the ground-state electron configuration of a complex we must
apply the building-up principle (Pauli exclusion principle)
Ti2+ (3d2)
2
t2g
2 x (0.4∆O) = 0.8∆O
LFSE = 0.8∆O
0.6
V2+ (3d3)
3
-0.40 t2g
3 x (0.4∆O) = 1.2∆O
LFSE = 1.2∆O
This additional stability, relative to the barycentre is called the ligand-field

stabilization energy (LFSE)
Ligand-field stabilization energies
To predict the ground-state electron configuration of a complex we must
apply the building-up principle (Pauli exclusion principle).
Cr2+ (3d4)
4
[Cr(CN)6]4- t2g
4 x (0.4∆O) = 1.6∆O
LFSE = 1.6∆O - P
0.6
Cr2+ (3d4)
3 1
[Cr(OH2)6]2+ t2g eg
-0.40
3 x (0.4∆O) - 1 x 0.6∆O = 0.6∆O
LFSE = 0.6∆O
This additional stability, relative to the barycentre is called the ligand-field

stabilization energy (LFSE)
[Fe(H2O)6]2+
Small Δ
d6 High spin
d4 d5 d6 d7 Pale blue
High spin
d1 d2 d3 d8 d9
[Fe(CN)6]4-
Large Δ
d6 Low spin
d4 d5 d6 d7
Yellow
Low spin
The high spin (small Δ) and low spin (large Δ) possibilities for d4-d7 octahedral
complexes
Ligand-field stabilization energies for octahedral complexes
The high spin (small Δ) and low spin (large Δ) possibilities for d4-d7 octahedral
complexes
Excercise
Determine the LFSE for the following octahedral ions from first principles:
(a) high-spin d5, (b) high-spin d6, (c) low-spin d6, (d) d9
Tetrahedral complexes
Four-coordinate tetrahedral complexes are second only in abundance to

octahedral complexes for the 3d metals
(dxy, dyz, dzx)
4
≈ Δo
9
(dx 2−y 2, dz 2)
The orbital energy level diagram used in the application of the building-
up principle in a crystal-field analysis of a tetrahedral complex
The effect of a tetrahedral crystal field on a set of d orbitals is to split

them into two sets; the e pair (which point less directly at the ligands) lie
lower in energy than the t2 triplet
Ligand-field stabilization energies for tetrahedral complexes

4
ΔT ≈ Δo
9
The pairing energy is invariably more unfavourable than ∆T, and

normally only high-spin tetrahedral complexes are encountered
Square planar complexes
Although a tetrahedral arrangement of four ligands is the least sterically

demanding arrangement, some complexes exist with four ligands in an
apparently higher energy square-planar arrangement
The d orbital splitting in an octahedral

crystal field
d x2-y2, d z2 (eg)
3Δ
5
-2 Δ
5
dxy, dyz, dzx (t2g)
There are two conceptually different approaches to square planar

complexes. One may regard the d orbital splitting as being that obtained
when two trans ligands are simultaneously removed from an octahedral
complex.
Square planar complexes
A square planar complex

can be derived from an
octahedral complex by
the removal of two
ligands
Magnetic properties of transition metal complexes
Published in: J. Am. Chem. Soc. 2011, 133, 16243-16250.


Crystal structure of the

paramagnetic material

F F
F F
F F
R
F F N
R N
N 365 nm N
F F N
N R
455 nm N
N Ni N R
N N
F N F
F F
F F Square planar
F F
F F crystal field
b1g
eg
a1g
In this case, this

phenomenin is
dominated by the b2g
8
steric hindrance
d
t2g
eg
Octahedral Paramagnetic
Square planar Diamagnetic
Paragmagnetic Diagmagnetic
Crystal field splitting diagrams for some common fields
referred to a common barycentre
Ligand-field theory
can be used to interpret

1. magnetic,
2. spectroscopic,
3. thermochemical properties
Crystal-field theory however,
does not take into account
the overlap of ligand and
metal atom orbitals
is an application of
molecular orbital theory that
concentrates on the d
Ligand-field theory orbitals of the central metal
atom, provides a more
substantial framework for
understanding the origins of
∆O
Ligand-field theory
In an octahedral complex in which each ligand (L) has a single valence
orbital directed towards the central metal atom (M); each of these
orbitals has local symmetry with respect to the M-L axis
Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd

C 42
A1g 1 1 1 1 1 1 1 1 1 1 x 2 + y 2 + z2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 2z2 - x2 - y2, x2 – y2
T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1
Character table of point group Oh

Ligand-field theory
Six symmetry-adapted linear combinations of the six ligand

orbitals can also be formed
Six symmetry-adapted linear combinations (SALC)
a1g : σ1 + σ2 + σ3 + σ4 + σ5 + σ6 (1)
t1u : σ1 − σ3, σ2 − σ4, σ5 − σ6 (3)
eg : σ1 − σ2 + σ3 − σ4, 2σ6 + 2σ5 − σ1 − σ2 − σ3 − σ4 (2)

Attention: There is no combination of ligand σ orbitals that has the symmetry
of the metal t2g orbitals, so the latter do not participate in σ bonding
Ligand-field theory
Metal-Ligand σ Interactions
The ligand σ group orbitals are of A1g,

Eg and T1u symmetries and each set
will overlap with metal orbitals of
the same symmetries, so that the 4s
(a1g), 4p (t1u) and 3d (eg) orbitals of
the metal will be involved in a
bonding
Ligand-field theory
Metal-Ligand σ Interactions
Ligand-field theory
Molecular orbitals are formed by combining SALCs and metal atomic

orbitals of the same symmetry
Ligand-field theory
The metal orbitals and the six SALCs of the ligand orbitals can overlap to
give 12 molecular orbitals in total: 6 bonding orbitals and 6 anti-bonding
orbitals
6 anti-bonding orbitals
The three triply degenerate

metal t 2g orbitals remain
Electrons of nonbonding and fully
the metal localized on the metal atom
6 bonding orbitals
Electrons of the ligand
Using a photoelectron spectrum to obtain
information about a complex
The photoelectron spectrum of gas-phase [Mo(CO)6] is shown in the figure

bellow. Use the spectrum to infer the energies of the molecular orbitals of
the complex
Using a photoelectron spectrum to obtain
information about a complex
The photoelectron spectrum of gas-phase [Mo(CO)6] is shown in the figure

bellow. Use the spectrum to infer the energies of the molecular orbitals of
the complex
Mo(0)
6 e-
CO (strong flied)
6
t2g
6 x CO
12 e-
2 6 4
a1g t1u eg
Ligand-field theory
Metal-Ligand π Interactions
If the ligands in a complex have orbitals with local π symmetry with
respect to the M-L axis, they may form bonding and antibonding π
orbitals with the metal orbitals
For an octahedral complex the

combinations that can be formed
from the ligand π orbitals include
SALCs of t2g symmetry
The π overlap that may occur between

a ligand p orbital perpendicular to the
M-L axis and a metal dxy orbital
Ligand-field theory
π-Donor ligands decrease Δ0 whereas π-acceptor ligands increase Δ0 ;
the spectrochemical series is largely a consequence of the effects of π
bonding when such bonding is feasible
Two considerations
Depending on the relative 1. the resulting bonding molecular

energies of the ligand and metal orbitals are significantly lower in
orbitals, the energies of the now energy and the antibonding
molecular orbitals are
molecular t2g orbitals lie above or
significantly higher in energy than
below the energies they had as
the atomic orbitals
nonbonding atomic orbitals 2. atomic orbitals with similar
e n e r g i e s i n t e r a c t s t r o n g l y,
whereas those of very different
energies mix only slightly even if
their overlap is large
Ligand-field theory
π donor ligands
A π-donor ligand is a ligand that, before any bonding is considered, has
filled orbitals of π symmetry around the M-L axis
Such ligands include Cl-, Br-, OH-, O2-

and even H2O
the bonding combination lies lower

π-donor ligands
than the ligand orbitals and the
decrease Δo antibonding combination lies above the
energy of the d orbitals of the free
metal atom
The electrons supplied by the ligand π

orbitals occupy and fill the bonding
combinations, leaving the electrons
originally in the d orbitals of the
central metal atom to occupy the
The effect of π bonding on the ligand- antibonding t2g orbitals
field splitting parameter. Only the π
orbitals of the ligand are shown
Ligand-field theory
π aceptor ligands
A π-acceptor ligand is a ligand that has empty π orbitals that are available
for occupation
Such ligands include CN-, CO, N2 and

even PR3
Because the π-acceptor orbitals on

most ligands are higher in energy than
the metal d orbitals, they form
π-acceptor ligands molecular orbitals in which the bonding
increase Δo t2g combinations are largely of metal d-
orbital character
These bonding combinations lie lower

in energy than the d orbitals
themselves
Ligands that act as π acceptors
increase Δo . Only the π orbitals of the
ligand are shown
Ligand-field theory
Weak Field Complexes
➢ Weak field complexes are those for which the crystal splitting Δ, is
smaller than the electron-repulsion and -exchange energies.
➢ The most important is the attraction between an electron and the

nucleus. Next, the effects of interelectron repulsion (this includes the
exchange energy) are considered, then the coupling between the spin
and orbital motion of the electron (spin-orbit coupling) and so on.
➢ The most stable electron arrangement in the free ion, which will be
preserved in weak field complexes, is one in which electron-electron
repulsion is a minimum.
➢ The electrons are as far apart as is possible. This will be when they
occupy different orbitals as much as is possible and this, in turn,
means that the term of highest spatial (orbital) and spin multiplicity
will be the ground state.
Spectroscopic Terms
➢ the symbols A1g, A2g, Eg, T1g and T2g will be encountered with a spin state
designated, for example, 2Eg ('doublet ee gee') and 3T1g.
2
➢ We shall refer to 𝑡2𝑔, ('tee two gee two'), for example when talking about
two electrons in a set of t2g orbitals (other books may refer to this as
3
(t2g)2). Symbols such as 𝑡2𝑔 or (t2g)3 indicate that the set of three orbitals
labelled t2g are occupied by three electrons.
➢ We talk of 'the P term arising from the p1 configuration', or 'the P term

arising from the d2 configuration' and so on.
Spectroscopic Terms
The spectrum of the d3 complex [Cr(NH3)6]3+

Spectroscopic Terms
The electronic configuration is an incomplete description of the

arrangement of electrons in atoms
In the configuration 2p2:

1. The two electrons might occupy orbitals with different orientations
(ml = 1, 0, -1)
2. the designation 2p2 tells us nothing about the spin orientations of

the two electrons ms = +1/2 or –1/2
The different ways in which the electrons can occupy the

orbitals specified in the configuration are called the
microstates of the configuration
Both electrons occupy an orbital with ml = +1, but
(1+, 1-)
do so with opposite spins
2p2
Both electrons have ms = +1/2 but one occupies
(-1+, 0+) the 2p orbital with ml = -1 and the other occupies
the orbital with ml = 0
Spectroscopic Terms
If electron-electron repulsions are taken into account, we obtain

the spectroscopically distinguishable energy levels called terms
For light atoms (3d configurations) the order of importance is S > L.
For heavy atoms, the spin and orbital angular momenta of individual
electrons are strongly coupled together by spin-orbit coupling (J = total
angular moment).
Russel-Saunders Coupling
The process of combining electron angular momenta by summing first
the spins, then the orbital momenta, and finally combining the two
resultants is called Russell-Saunders coupling
The coupling scheme most appropriate to heavy atoms (that is, atoms of
the 4d and 5d series of elements) is called jj-coupling
Spectroscopic Terms
According to the Clebsch-Gordan series, the possible values of L

and S are
L = l1 + l2, l1 + l2 - 1, ... , |l1 - l2|
S = s1 + s2, s1 + s2 - 1, ... , |s1 - s2|
For example, an atom with configuration d2 (l1 = 2, l2 = 2)

can have the following values of L:
L = 2 + 2, 2 + 2 - 1, ... , |2 - 2| = 4, 3, 2, 1, 0
The total spin (because s1 = 1/2 , s2 = 1/2) can be

S = 1/2 + 1/2, 1/2 + 1/2 - 1, ... , |1/2 – 1/2| = 1, 0
Spectroscopic Terms
Once L and S have been found, we can write down the

allowed values of the quantum numbers ML and MS,
ML = L, L - 1, ... , -L (2L + 1 values of ML)
MS = S, S - 1, ... , -S (2S + 1 values of Ms)
If one electron has the quantum number ml1 and the

other has ml2, then ML = ml1 + ml2
Similarly, MS = ms1 + ms2
(0+, -1- ) is a microstate with ML = 0 -1 = -1 and MS = 1/2 +(-1/2) = 0

Spectroscopic Terms
By analogy with the notation s, p, d, ... for orbitals with

l = 0, 1, 2,..., the total orbital angular momentum of an
atomic term is denoted by the equivalent uppercase
letter:
L=0 1 2 3 4…
S P D F G … then alphabetical (omitting J)
The total spin is normally reported as the value of 2S + 1,

which is called the multiplicity of the term:
S=0 1/2 1 3/2 2 L=1

2S + 1 = 1 2 3 4 5 3P
S=1
singlet doublet triplet
Spectroscopic Terms
For light metals (3d)
For heavy metals (4d and 5d)
J = (L + S), (L + S - 1) ... |L - S|
Spectroscopic Terms
For light metals (3d)
For heavy metals (4d and 5d)
J = (L + S), (L + S - 1) ... |L - S| MJ = J, J-1 … -(J-1), -J

Spectroscopic Terms
Determining the number of microstates

Spectroscopic Terms
For Hydrogen (Z = 1): 1s1
The complet spectroscopic term: 2S1/2

Spectroscopic Terms
For Boron (Z = 5): 1s22s22p1
L = 1 (a P term)
S = 1/2: (2S+1)=2 (doublet)
J = (L+S), (L+S-1) = 3/2, 1/2
Spectroscopic
terms: 2P3/2 or 2P1/2
Spectroscopic Terms
What about de relative energy of the terms
Relative energy
3F < 1D 3F < 3P
S=1 S=0 L=3 L=1

Spectroscopic Terms
Relative energy
C: 1s2 2s2 2p2 O: 1s2 2s2 2p4
3P0 < 3P1 3P1 < 3P0
S=1 S=1 S=1 S=1

L=1 L=1 L=1 L=1
J=0 J=1 J=1 J=0
Spectroscopic Terms
For Boron (Z = 5): 1s22s22p1
Spectroscopic
terms: 2P3/2 or 2P1/2
For the p1 configuration, the p level is less than half-filled, and

therefore the ground state level is the one with the lower value
of J, i.e. 2P1/2.
Spectroscopic Terms

For Carbon (Z = 6): 1s22s22p2
Spectroscopic terms:
1D
2
➢ The energy ordering is

3P < 3P < 3P < 1D < 1S
0 1 2 2 0
➢ The ground state is the 3P0 term
3P , 3P , 3P
2 1 0
1S
0
Spectroscopic Terms

The spin multiplicity rule is fairly reliable for predicting the
ordering of terms, but the ‘greatest L’ rule is reliable only for
predicting the ground term, the term of lowest energy.
For example, for d 2 the rules

predict the order:
Relative Energy
3F < 3P < 1G < 1D < 1S
but the order observed

(experimentally) for Ti 2+ from
spectroscopy is
3F < 1D < 3P < 1G < 1S

Spectroscopic Terms
Identifying the ground term of a configuration

Normally, all we want to know is the identity of the ground
term of an atom or ion.
1. Identify the microstate that has the highest value of MS.
2. Identify the highest permitted value of ML for that

multiplicity.
Example:
What is the ground term of the configurations
(a) 3d5 of Mn2+ and (b) 3d3 of Cr3+?
S = 5/2
Multiplicity = 6
d5 configuration 6S
ml = +2, +1, 0, -1, -2
ML = Σml = 0
L=0
Spectroscopic Terms
Identifying the ground term of a configuration

Normally, all we want to know is the identity of the ground
term of an atom or ion.
1. Identify the microstate that has the highest value of MS.
2. Identify the highest permitted value of ML for that

multiplicity.
Example:
What is the ground term of the configurations
(a) 3d5 of Mn2+ and (b) 3d3 of Cr3+?
S = 3/2
Multiplicity = 4
d3 configuration 4F
ml = +2, +1, 0
ML = Σml = 3
L=3
Spectroscopic Terms
➢ A crucial factor turns out to be the number of unpaired

electrons, n, associated with each term and this is
indicated by the number (n + 1) as a superscript thus: 2P,
3D and so on.
➢ An F term splits up into either T1u, T2u and A2u or T1g, T2g
and A2g subsets. Which of these is correct is determined
by the g or u nature of the configuration from which the F
term is derived.
➢ Because f orbitals are u in character the 2F term

corresponding to an f1 configuration splits up into 2T1u,
2T
2u and A2u components. Similarly, the F term derived
2 3
from the d2 configuration splits into 3T1g, 3T2g and 3A2g

components because the d orbitals are g in character.
Crystal field components of the ground and some excited terms

of dn (n = 1-9) configurations
d1 configuration
2D
Ground term Excited term
term 2T 2E
2g g
We speak about
electrons
(a) Ground and (b) excited states derived from the d1 configuration in an
octahedral crystal field
1
As a d1 configuration gives rise to a 2D term, the 𝑡2𝑔 configuration gives rise to
a 2T2g term. Similarly, the (excited) 𝑒𝑔1 configuration gives rise to a 2Eg term.
We conclude that the 2T2g term is the more stable because it means that the
solitary d electron is in the t2g orbitals.
d4 configuration
5D 5E 5T
term g 2g
We speak about holes
(a) Ground and (b) an excited state with the same spin multiplicity, derived
from the d4 configuration in an octahedral crystal field.
The most stable situation is that in which the hole is in the eg orbitals. The
ground term is therefore 5Eg.
In the d4 case, therefore, the splitting of the Eg and T2g levels is the inverse
of that in the d1 case.
d6 configuration
5D 5T 5E
term 2g g
We speak about
electrons
(a) Ground and (b) lowest excited state of the same spin multiplicity, derived
from the d6 configuration in an octahedral crystal field.
It differs from spherical symmetry by the presence of a single electron,

which is more stable when it is in the t2g orbitals.
The splitting therefore follows the d1 case, the 5T2g term being more stable
than the 5Eg term by an energy Δ.
d9 configuration
2E 2T
2D term g 2g
We speak about holes
(a) Ground and (b) excited state derived from the d9 configuration in an
octahedral crystal field.
The 2D term arising from the d9 configuration differs from spherical

symmetry by the presence of a hole in the eg orbitals in the ground state.
The ground state is therefore of 2Eg symmetry and the excited state, at an
energy of Δ above, is of 2T2g symmetry.
d2 configuration
3F
Ground term Excited term Excited term
term 3T 3T 3A
1g 2g 2g
We speak about
electrons
(a) Ground and (b, c) two excited state configurations of a d2 ion in an

In the ground term derived from the 3F term of the d2 configuration

we will find that there are two electrons in the t2g orbitals.
d3 configuration
4F term Ground term Excited term Excited term
4A 4T 4T
2g 2g 1g
We speak about
holes

In the ground term derived from the 4F term of the d3 configuration

we will find that there are two holes in the eg orbitals.
d7 configuration
4F term 4T 4T 4A
1g 2g 2g
We speak about
electrons
(a) Ground and (b, c) two excited state configurations of a d7 ion in

an octahedral crystal field.
The 4F term derived from the d7 configuration gives rise to an excited 4T2g
and 4A2g terms, with two holes occupying the t2g orbitals
The 3F term derived from the d8 configuration gives rise to an excited 3T1g
term, two holes occupying the t2g orbitals
d8 configuration
3F term 3A 3T 3T
2g 2g 1g
We speak about
holes

d5 configuration 6S term
The 6S ground state, which is derived from d5 configuration, is orbitally non-

degenerate and so no crystal field splitting can occur. The behavior of this 6S
term parallels that of an s orbital and becomes 6A1g in an octahedral crystal
field
The splitting of the weak field dn (n = 1-9) ground state terms in an

octahedral crystal field
The splitting of the weak field dn (n = 1-9)

ground state terms in an octahedral crystal field
Electronic Spectra
The broadness is a consequence of the

Franck–Condon approximation which
states that electronic transitions are very
much faster than nuclear motion
400 nm 25 000 cm-1

200 nm 50 000 cm-1
Absorptions arise from transitions

between electronic energy levels:

Unidad 2 - Parte 1 - Teoría Del Campo Cristalino, Espectroscopia Electrónica

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Universidad del Valle

Prof. Renso Visbal Acevedo Departamento Química

Mixed valence [CoFe] complexes and

When the complex was irradiated (λ =

Light-Induced Spin Change by Photodissociable External

Published in: J. Am. Chem. Soc. 2011, 133,

A set of metal p orbitals in an octahedral crystal field

The dx2-y2 and dz2 orbitals in an octahedral crystal field

In an octahedral crystal field the f orbitals of a metal atom

In an octahedral crystal field the f orbitals of a metal atom

The orientation of the five d orbitals with respect to the

The mean energy remains

The energies of the d orbitals in an octahedral crystal field

dxy, dyz, dzx (t2g)

The d orbital splitting in an octahedral

Δ value for metals of the first raw:

This value is up to twice for second The optical absorption

Values are in cm1-; entries in parentheses are for low-spin complexes

This additional stability, relative to the barycentre is called the ligand-field

This additional stability, relative to the barycentre is called the ligand-field

Four-coordinate tetrahedral complexes are second only in abundance to

(dxy, dyz, dzx)

The effect of a tetrahedral crystal field on a set of d orbitals is to split

Ligand-field stabilization energies for tetrahedral complexes

The pairing energy is invariably more unfavourable than ∆T, and

Although a tetrahedral arrangement of four ligands is the least sterically

The d orbital splitting in an octahedral

dxy, dyz, dzx (t2g)

There are two conceptually different approaches to square planar

A square planar complex

Published in: J. Am. Chem. Soc. 2011, 133, 16243-16250.

Published in: J. Am. Chem. Soc. 2011, 133, 16243-16250.

Crystal structure of the

Published in: J. Am. Chem. Soc. 2011, 133, 16243-16250.

In this case, this

can be used to interpret

Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd

T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)

T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

Character table of point group Oh

Six symmetry-adapted linear combinations of the six ligand

Six symmetry-adapted linear combinations (SALC)

t1u : σ1 − σ3, σ2 − σ4, σ5 − σ6 (3)

eg : σ1 − σ2 + σ3 − σ4, 2σ6 + 2σ5 − σ1 − σ2 − σ3 − σ4 (2)

The ligand σ group orbitals are of A1g,

Molecular orbitals are formed by combining SALCs and metal atomic

The three triply degenerate

The photoelectron spectrum of gas-phase [Mo(CO)6] is shown in the figure

The photoelectron spectrum of gas-phase [Mo(CO)6] is shown in the figure

For an octahedral complex the

The π overlap that may occur between

Depending on the relative 1. the resulting bonding molecular

Such ligands include Cl-, Br-, OH-, O2-

the bonding combination lies lower

The electrons supplied by the ligand π

Such ligands include CN-, CO, N2 and

Because the π-acceptor orbitals on

These bonding combinations lie lower

➢ The most important is the attraction between an electron and the

➢ We talk of 'the P term arising from the p1 configuration', or 'the P term

The spectrum of the d3 complex [Cr(NH3)6]3+

The electronic configuration is an incomplete description of the

In the configuration 2p2: