Bohr's model of atom and explanation of hydrogen spectra

In 1913, Neils Bohr proposed a model of an atom based on the Planck's quantum theory of
radiation. The basic postulates of Bohr's theory are:
 An atom consists of a small, heavily positively charged nucleus around which electrons
revolve in definite circular paths called orbits.
 These orbits are associated with definite energies called energy shells/energy levels. They
are designated as K, L, M, N, …. etc. shells or numbered as 1, 2, 3, 4, …..etc. from the
nucleus.
 As long as the electron remains in a particular orbit /energy shell its energy remains
constant. This accounts for the stability of an atom.
 Only those orbits are permitted in which angular momentum of the electron is a whole

number multiple of where h is Plancks constant. Any moving body taking a circular orbit
has an angular momentum equal to the product of its mass (m), velocity of movement (v) and
radius of orbit (r). In other words the angular momentum of an electron

Thus,

This postulate introduces the concept of quantization of angular momentum.

 Electrons can either lose or absorb energy abruptly, when they jump from one energy
level to another. For instance when an electron moves from the 'normal or ground state - E1'
of an atom i.e., the state of lowest energy as required by its 'n' and 'l' values, to a higher level,
it causes the atom to be in its 'excited state - E2' i.e., where electrons in an atom occupy
energy levels higher than those permitted by its 'n' and 'l' values. The reverse is also true and
the change in energy isDE,
DE = E2 - E1 = hn
Fig: 3.13 - Energy changes in an electron jump
Bohr's atomic model explained successfully:
 The stability of an atom. Bohr postulated that as long an electron remains in a particular
orbit it does not emit radiation i.e. lose energy. Hence it does not become unstable.
 The atomic spectrum of hydrogen was explained due to the concept of definite energy
levels. The one electron of hydrogen being closest to the nucleus is in its lowest energy shell
(n =1) or normal ground state. It can absorb a definite amount of energy and jump to a higher
energy state. This excited state being unstable, the electron comes back to a lower energy
level.
When the energy emitted during transition, strikes a photographic plate, it gives its impression in
the form of a line. This difference is also the energy of photon expressed as E2 - E1 = hn.
The frequency of the emitted radiation is:

Since E2 and E1 have only definite values and are characteristic of energy levels of atoms, the
values of 'n' will also be definite and characteristic of the atoms. Thus each transition will
produce a light of definite wavelength, which is observed as a line in the spectrum.
For example, if the electron jumps down from the third to the first energy level having energies
E3 and E1 respectively, then the wavelength of the spectral line would be

Similarly, when the electron jumps down from the fourth to the first energy level having energies
E4 and E1 respectively or from the fifth to the second i.e., E5 and E2, then we have

These will give different lines in the spectrum of the atom corresponding to different transitions
having definite wavelengths.
 The sample of hydrogen gas contains a large number of atoms and when energy is
supplied, the electrons in different hydrogen atoms absorb different amounts of energies.
These are raised to different energy states. For example, the electrons in some atoms may
jump to second energy level (L), while in others it may be to the third (M), fourth (N) or fifth
(O) and so on. These electrons come back from the higher energy levels to the ground state in
one or more jumps emitting different amount of energies.
Fig: 3.14 - Different routes to the ground state from n = 4
Different lines depending upon the difference in energies of the levels concerned can be
summarized in the form of series named after the scientists who have discovered them.
Lyman series from n = 2, 3, 4, 5……to n = 1
Balmer series from n = 3, 4, 5, 6……to n = 2
Paschen series from n = 4, 5, 6, 7……to n = 3
Brackett series from n = 5, 6, 7, 8……to n = 4
Pfund series from n = 6, 7, 8, 9……to n = 5.
 The energy of the electron in a particular orbit of hydrogen atom could be calculated by
Bohr's theory. The energy of the electron in the 'nth' orbit has been found to be

where 'm' is the mass and 'e' is the charge of the electron. The energy expression for hydrogen
like ions such as He, Li can be written as:

where 'Z' is the nuclear charge, which is equal to atomic number.

Problems
7. If the energy difference between the electronic states of hydrogen atom is 214.68 kJ mol-1,
what will be the frequency of light emitted when the electron jumps from the higher to the lower
energy state? (Planck's constant = 39.79 x 10-14 kJ mol-1)
Solution
The frequency (n) of emitted light is related to the energy difference of two levels (DE) as

E = 214.68 kJ mol-1, h = 39.79 x 10-14 kJ mol-1

= 5.39 x 1014 s-1

8. The wavelength of first spectral line in the Balmer series is 6561 Å units. Calculate the
wavelength of the second spectral line in Balmer series.
Solution
According to Rydberg equation:

For the first line in Balmer series, n1 = 2, n2 = 3

For the second line in Balmer series, n1 = 2, n2 = 4

Dividing equations (i) by (ii)

A spectrum is an assembly of energy levels in the form of radiations emitted by an atom in its
excited state. Every atom gives discontinuous line spectra. Each line in the spectra corresponds
to a specific wavelength and it is unique to a given element. No two elements give same pattern
of lines in their spectra.
Atomic emission spectra
When a substance is heated to a high temperature, the atoms in the vapours get energized. These
energized atoms then return to the ground state by emitting electromagnetic radiations of certain
definite wavelength. A series of bright lines separated from each other by dark spaces is obtained
and this is called atomic emission spectra.

Fig: 3.9 - Mechanism of emission spectra

Atomic absorption spectra
When the atomic vapours from a sample are placed in the path of white light from an arc lamp, it
absorbs the light of certain characteristic wavelengths and the light of other wavelengths get
transmitted. In such conditions a series of dark lines on a white background are formed. This is
called an absorption spectrum.
The dark lines in the absorption spectrum and the bright lines in the emission spectrum of a
given element appear at the same wavelength.
Fig: 3.10 - Comparison of Absorption and emission spectra of sodium vapour
Since each element gives a definite pattern of lines at certain definite frequencies or
wavelengths, the atomic spectra is used in chemical analysis to identify and estimate the
elements present in any sample.
Atomic spectra of hydrogen atom
Hydrogen is the simplest element with its atom having only one electron. Hence, the atomic
spectrum of hydrogen has played a significant role in the development of atomic structure. In the
emission spectrum of hydrogen, when an electric discharge is passed through hydrogen gas, the
molecules of hydrogen break into atoms. The hydrogen atoms get energized and go into an
excited state. The excited atoms then return to the ground state by emitting light. Hydrogen
atoms emit bluish light. On passing this light through a prism, a discontinuous line spectrum
consisting of several sharp lines is obtained. This is the line spectrum of hydrogen.
Four sharp coloured lines were observed in the visible region of this spectrum by Balmer, in the
ultra violet region by Lyman, in the infrared region by Paschen, Brackett and Pfund. These series
of lines are named after these scientists who discovered them. Balmer expressed these lines in
terms of inverse of their wavelength ( ) by a mathematical relation, which was later modified by
Rydberg.

where 'RH' is the Rydberg's constant and 'n1', 'n2' are integers with values equal to or greater than
3 and 'l' is the wavelength.

Fig: 3.11 - Line spectrum of hydrogen atom

Problem
6. Calculate the wavelength of the spectral line when the electron in the hydrogen atom
undergoes a transition from 4th energy level to 2nd energy level. What is the colour of the
radiation?
Solution
According to Rydberg's equation
here, n1 = 2, n2 = 4 and R = 109678 cm-1

l = 486 x 10-9 m = 486 nm.

The Russell Saunders Coupling Scheme

Review of Quantum Numbers

Electrons in an atom reside in shells characterised by a particular value of n, the Principal

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),
traditionally termed s, p, d, f, etc. orbitals.

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.

A quantum mechanics approach to determining the energy of electrons in an element or 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.

There are thus (2l +1) values of ml for each l value,

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, originally conceived as the rotation of a
particle around some axis. Electrons are not literally spinning balls of charge, but they do have
intrinsic angular momentum that may be regarded as being generated by a circulating flow of
energy in the wave field of the electron. Likewise, the magnetic moment may be regarded as
generated by a circulating flow of charge in the wave field. This provides an intuitively
appealing picture and establishes that neither the spin nor the magnetic moment are "internal" -
they are not associated with the internal structure of the electron, but rather with the structure of
its wave field. American Journal of Physics 54, 500 (1986)
Spin quantum numbers may take half-integer values, ms is either + ½ or - ½.

In summary then, each electron in an orbital is characterised by four quantum numbers:

Quantum Numbers

symbol description range of values

Principal Quantum Number -

n largely governs size of orbital and 1,2,3 etc
its energy

Azimuthal/Orbital Quantum
(0 ≤ l ≤ n-1)
Number - largely determines shape
l for n = 3 then l
of subshell
= 0, 1, 2 (s, p, d)
0 for s orbital, 1 for p orbital etc

Magnetic Quantum Number - l ≥ ml ≥ -l

ml orientation of subshell's shape for l = 2, then ml
for example px with py and pz = 2, 1, 0, -1, -2

either + ½ or -
ms Spin Quantum Number ½ for single
electron
Russell Saunders coupling

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.

The interactions that can occur are of three types.

 spin-spin coupling
 orbit-orbit coupling
 spin-orbit coupling

There are two principal coupling schemes used:

 Russell-Saunders (or L - S) coupling

 and j - j coupling.

In the Russell Saunders scheme (named after Henry Norris Russell, 1877-1957 a Princeton
Astronomer and Frederick Albert Saunders, 1875-1963 a Harvard Physicist and published in
Astrophysics Journal, 61, 38, 1925 ) it is assumed that:
spin-spin coupling > orbit-orbit coupling > spin-orbit coupling.

This is found to give a good approximation for first row transition series where spin-orbit (J)
coupling can generally be 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:

Total Orbital Momentum

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.

Terms for 3dn free ion configurations

# of # of
Ground
Configuration quantum energy Excited Terms
Term
states levels

d1,d9 10 1 2
D -

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

4
P, 2H, 2G, 2F, 2 x 2D,
d3,d7 120 8 4
F 2
P

3
H, 3G, 2 x 3F, 3D, 2 x
d4,d6 210 16 5
D 3
P, 1I, 2 x 1G, 1F, 2 x
1
D, 2 x 1S
 4
G, 4F, 4D, 4P, 2I, 2H, 2
d5 252 16 6
S x 2G, 2 x 2F, 3 x 2D, 2P,
2
S

Note that dn gives the same terms as d10-n

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 multiplicity, 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

d3 ↑ ↑ ↑ 3 3/2 4
F

d4 ↑ ↑ ↑ ↑ 2 2 5
D

d5 ↑ ↑ ↑ ↑ ↑ 0 5/2 6
S

d6 ↑↓ ↑ ↑ ↑ ↑ 2 2 5
D

d7 ↑↓ ↑↓ ↑ ↑ ↑ 3 3/2 4
F

d8 ↑↓ ↑↓ ↑↓ ↑ ↑ 3 1 3
F

d9 ↑↓ ↑↓ ↑↓ ↑↓ ↑ 2 1/2 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.
7
For a d 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

Total value of L is therefore +4 +2 +0 -1 -2 or L=3.

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.

The other thing to note is the idea of the "hole" approach.

1 9
A d configuration can be treated as similar to a d configuration. In the first case there is 1
electron and in the latter there is an absence of an electron ie a hole.

The overall result shown in the Table above is that:

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 Crystal Field Splitting of Russell-Saunders terms

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 Δ oct
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.

The Crystal Field Splitting of Russell-Saunders

terms
in high spin octahedral crystal fields.

Russell-Saunders Crystal Field

Terms Components

S (1) A1g

P (3) T1g

D (5) Eg , T2g

F (7) A2g , T1g , T2g

G (9) A1g , Eg , T1g , T2g

H (11) Eg , 2 x T1g , T2g

I (13) A1g , A2g , Eg , T1g , 2 x 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 Explanation

for atomic and molecular
 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.

Spectroscopy of First Row Transition Metal Complexes

Crystal Field Theory copes reasonably well for d1 (d9) systems but not for multi-electron
systems, which are the more common. To deal with these systems we need to introduce a new
concept, that of the electronic state.
Electronic configurations refer to the way in which the electrons occupy the d orbitals, so for
Ti(III) we write an electronic configuration of [Ar] 3d1 and in an octahedral crystal field the
lowest energy configuration would be written as t2g1 eg0.
The electronic state refers to energy levels available to a group of electrons. This is much more
complex than the single electron case since not only is it necessary to consider the crystal field
effects of the repulsion of the metal electrons by the ligand electrons, but it is necessary to
include the interactions between the electrons themselves.
When describing electronic configurations, lower case letters are used, thus t2g1 etc.
For electronic states, upper case (CAPITAL) letters are used and by analogy, a T state is triply
degenerate. Subscripts 1 and 2 are used to distinguish states of like degeneracy and g and u
subscripts indicate the presence of a centre of symmetry eg. T1g, T2g, T1u and T2u.
These symbols are further modified to show the spin multiplicity of the electronic state using the
Russell-Saunders Notation.
1
If we consider the Ti(III) case, the electronic configuration is d . In an octahedral crystal field
this would give rise to a t2g1 arrangement and the excitation of the low lying electron to the
higher level would then give an eg1 arrangement.
Only one d-d transition is expected and this roughly corresponds to what is observed for Ti(III)
complexes, although it is somewhat more complicated due to Jahn-Teller considerations. At the
high energy end of the spectrum, the presence of a charge transfer band should be noted as well.
The origin of this will not be covered in detail in this course.
One approach taken when we consider the Russell-Saunders scheme with the various electronic
states makes use of what are called Orgel diagrams. The relevant Orgel diagram for the D ground
state is given below:
oct 4,9 tet 1,6 <-------------------------------------------> oct 1,6 tet 4,9

For a Fe(II) high spin octahedral complex we would write the free ion electronic configuration as
d6 and in the octahedral crystal field it would be described as t2g4 eg2.
The Russell-Saunders scheme that takes into account the electron-electron interactions would be
described by a free ion ground state of 5D. In octahedral and tetrahedral crystal fields, this D
state is split into E(g) and T2(g) terms. To decide which side of the D Orgel diagram should be
applied to the interpretation can be quickly determined by looking at the electronic configuration
and noting that the ground state is triply degenerate and the excited state is doubly degenerate
(i.e. we must use the right-hand-side).
It is expected then that there should be 1 absorption band found in the electronic spectrum and
that the energy of the transition corresponds directly to Δ. The transition is written in a notation
that is read from right to left, which in this case is 5Eg ← 5T2g.
Spectroscopy of First Row Transition Metal Complexes - F ground states
We have already looked at Transition metal ion complexes with D ground states which accounts
for the d1, d4, d6 and d9 configurations.
2 3 7 8
We turn now to d , d , d and d configurations for which the ground state of the free ions are
given by Russell-Saunders F terms.

In octahedral and tetrahedral crystal fields, the F state is split into A2(g), T1(g) and T2(g) terms,
while the P term generates an additional T1(g) term. Once again we can make use of the analogy
to the splitting of orbitals in a crystal field so in this case we can look at how the f-orbitals lose
their 7-fold degeneracy in an octahedral field.

It should be noted that whenever the ground state is an F term there will be a P term found at
higher energy with the same spin multiplicity. The separation of these terms in the free ion is
measured in terms of the B Racah parameter and is equivalent to 15B (where B is usually around
1000 cm-1).

Once again, one approach taken to aid in the interpretation of these spectra is to use an Orgel
diagram. The relevant Orgel diagram for the F ground state is given below:
oct d3,d8 tet d2,d7 ←-----------------------------------→ oct d2,d7 tet d3,d8
ν1= 4/5 Δ + x
ν1 = Δ (T2g←A2g)
(T2g←T1g)

ν2 = 9/5 Δ + x
ν2 = 9/5 Δ - x
(A2g←T1g) OR ν2 = 3/5 Δ + 15B + 2x
(T1g←A2g)
(T1g(P)←T1g)

ν3 = 3/5 Δ + 15B
ν3 = 6/5 Δ + 15B + x
+ 2x (T1g(P)←T1g) OR ν3 = 9/5 Δ + x
(T1g(P)←A2g)
(A2g←T1g)

The lines showing the A2 and T2 terms are linear and depend solely on Δ. The "non-crossing
rule" results in the lines for the two T1 terms being curved to avoid each other and as a result this
introduces a "configuration interaction" in the transition energy equations.

That is, whenever there are lines with equivalent Russell-Saunders terms on the Orgel diagram
they are not allowed to cross and are found to diverge. All other lines are expected to be linear.

Visible spectra of some Cr(III) complexes

For Cr(III) complexes, we would start by writing the free ion electronic configuration as d3 and
in an octahedral crystal field this would be described as t2g3 eg0.
The Russell-Saunders scheme that takes into account the electron-electron interactions would be
described by a free ion ground state of 4F. To decide which side of the F Orgel diagram should
be applied to the interpretation can be quickly determined by looking at the electronic
configuration and noting that the ground state is singly degenerate (i.e. we need the left-hand-
side where the lowest term is A2).
It is expected then that there should be 3 absorption bands found in the electronic spectrum. The
energy of the first transition corresponds directly to Δ and the transition is written as 4T 2g ←
4A2g.
If we now consider the d2 electronic configuration, then the Russell-Saunders free ion ground
term state is a 3F. For an octahedral complex, the lowest energy state is a triplet which tells us
that we need to be using the right-hand-side of the F Orgel diagram.
The first transition is written as 3T2g ← 3T1g and the energy of this transition does NOT
correspond directly to Δ. It should be carefully noted that when using this side of the F-Orgel
diagram none of the expected transitions correspond exactly to Δ . Interpretation of d2
spectra are made even more complicated since as we increase the size of Δ we note that at some
point the 3T1g(P) and 3A2g lines cross. To determine the sequence of the transitions (that is
whether we are on the left-hand-side or right-hand-side of the intersection) normally requires that
all 3 absorption bands can be observed. This is often not the case and an alternative approach to
interpretation of these spectra is needed. One such approach makes use of what are known as
Tanabe-Sugano diagrams.

Interpretation of the spectra of first-row transition metal complexes using Tanabe-Sugano

diagrams

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 Δ. In practice, ignoring spin-forbidden lines, this is only
observed for those ions with D free ion ground terms i.e., d1, d9 as well as d4, d6.

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 free ion 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.

In the laboratory component of the course we will measure the absorption spectra of some
typical chromium(III) complexes and calculate the spectrochemical splitting factor, Δ. This
corresponds to the energy found from the first transition below 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).

For the d3 octahedral case, 3 peaks can be predicted and these would correspond to the following
transitions and energies:
4
1. T2g ← 4A2g transition energy = Δ
 4
2. T1g(F) ← 4A2g transition energy = 9/5 * Δ - C.I.
4
3. T1g(P) ← 4A2g transition energy = 6/5 * Δ + 15B' + C.I.

where C.I. is the configuration interaction arising from the "non-crossing rule".

Table 1. Peak positions for some octahedral Cr(III) complexes (in cm-
1
).

ν2/ ν1/
Complex ν1 ν2 ν3 Δ/B Ref
ν1 ν2

Cr3+ in emerald 16260 23700 37740 1.46 0.686 20.4 13

K2NaCrF6 16050 23260 35460 1.45 0.690 21.4 13

This
[Cr(H2O)6]3+ 17000 24000 37500 1.41 0.708 24.5
work

Chrome alum 17400 24500 37800 1.36 0.710 29.2 4

This
[Cr(C2O4)3]3- 17544 23866 ? 1.37 0.735 28.0
work

[Cr(NCS)6]3- 17800 23800 ? 1.34 0.748 31.1 4

This
[Cr(acac)3] 17860 23800 ? 1.33 0.752 31.5
work

[Cr(NH3)6]3+ 21550 28500 ? 1.32 0.756 32.6 4

[Cr(en)3]3+ 21600 28500 ? 1.32 0.758 33.0 4

[Cr(CN)6]3- 26700 32200 ? 1.21 0.829 52.4 4

For octahedral Ni(II) complexes the transitions would be:

 3
1. T2g ← 3A2g transition energy = Δ
3
2. T1g(F) ← 3A2g transition energy = 9/5 * Δ - C.I.
3
3. T1g(P) ← 3A2g transition energy = 6/5 * Δ + 15B' + C.I.

where C.I. again is the configuration interaction and as before the first transition corresponds
exactly to Δ.

For M(II) the size of Δ is much less than for M(III) 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).

ν1/
Complex ν1 ν2 ν3 ν1 Δ/B Ref
ν2

NiBr2 6800 11800 20600 1.74 0.576 5 13

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

[Ni(gly)3]- 10100 16600 27600 1.64 0.608 10.6 13

[Ni(NH3)6]2+ 10750 17500 28200 1.63 0.614 11.2 13

[Ni(en)3]2+ 11200 18350 29000 1.64 0.610 10.6 3

[Ni(bipy)3]2+ 12650 19200 ? 1.52 0.659 17 3

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 some octahedral V(III) complexes (in cm-1).

ν2/
Complex ν1 ν2 ν3 ν1/ν2 Δ/B Ref
ν1
 V3+ in Al2O3 17400 25200 34500 1.448 0.6906 30.90 13

[VCl3(MeCN)3] 14400 21400 ? 1.486 0.6729 28.68 4

K3[VF6] 14800 23250 ? 1.571 0.6365 24.78 4

Interpretation of the spectrum highlights the difficulty of using the right-hand side of the Orgel
diagram as previously noted. For d2 cases where none of the transitions correspond exactly to Δ
often only 2 of the 3 transitions are clearly observed and hence the calculations will have three
unknowns (Δ, B and C.I.) but only 2 energies to use in the the analysis.

The first transition can be unambiguously assigned as:

3
T2g ← 3T1g transition energy = 4/5 * Δ + C.I.

But, depending on the size of the ligand field ( Δ) the second transition may be due to:
3
A2g ← 3T1g transition energy = 9/5 * Δ + C.I.

for a weak field or

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

for a strong field.

The transition energies of these terms are clearly different and it is often necessary to calculate
(or estimate) values of B, Δ 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 Δ. In this case Δ is equal to
either:
25200 - 17400 = 7800 cm-1
or 34500 - 17400 = 17100 cm-1.
Given that we expect Δ 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 Δ. 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.

Using Tanabe-Sugano diagrams

The use of Orgel diagrams allows a qualitative description of the spin-allowed electronic
transitions expected for states derived from D and F ground terms. Only 2 diagrams are needed
for high spin d2-d9 and both tetrahedral and octahedral ions are covered.

Tanabe-Sugano diagrams were developed in the 1950's to give a semi-quantitative approach and
include both high and low spin ions and not only the spin-allowed transitions are shown but the
spin-forbidden transitions are displayed as well.

At first glance they can appear quite daunting, but in practice they are much easier to use for
interpreting spectra and provide much more information. The obvious differences are the
presence of the additional lines and that the ground state is shown as the base line along the X
axis rather than as a straight line or curve originating from the Y axis.

On the X axis Δ/B' is plotted while on the Y axis E/B' is plotted, where B' is the modified Racah
B parameter that exists in the complex.

A separate diagram is needed for each electronic configuration d2-d9 and for the d4-d7 cases both
the high spin and low spin electronic configurations are shown. The high spin is on the left-hand-
side of the vertical line on the diagram.

For the d2 case where it is difficult to use an Orgel diagram, the TS diagram is shown below.
3
The ground state is T1g which is plotted along the base line.
Note that the transitions that occur are dependent on the sizes of Δ and B and the A 2g term may
be either higher or lower than the T1g (P) term (depending on whether Δ/B' is greater than about
15).

For the V(III) aqua ion, transitions are observed at 17,200 and 25,600 cm-1 which are assigned to
the 3T2g ← 3T1g and 3T1g(P) ← 3T1g (F) respectively.
Interpretation requires taking the ratio of these frequencies and then finding the position on the
diagram where the height of the 3T1g(P) / 3T2g exactly matches that ratio.

For a ratio of 1.49, this is found on the diagram below at Δ/B' of 28.0.
Reading off the position on the Y axis for the three spin-allowed lines gives E/B' values of 25.9,
38.6 and 53 (3T2g, 3T1g and 3A2g)

To determine the value of Δ and B' is now relatively straightforward since from the first
transition energy of 17,200 cm-1 and the value of E/B' of 25.9 we can equate B' as:
B' = 17,200/ 25.9 or B' = 665 cm-1
Alternatively from the second transition energy of 25,600 cm-1 and the value of E/B' of 38.6 we
can equate B' as:
B' = 25,600/ 38.6 or B' = 663 cm-1 which is in excellent agreement with the value found from the
first transition.

The value of Δ can then be determined from the Δ/B' ratio of 28.0 and the value just calculated
for B' of 665 cm-1.
This gives Δ as 28.0 x 665 = 18,600 cm-1

The transition 3A2g ← 3T1g would be predicted to occur at 53 x 665 that is 35,245 cm-1 (or 284
nm) which is in the UV region and not observed. (Possibly obscured by charge transfer bands).

The values of Δ and B' can be compared to similar V(III) complexes and it should be noted that
in general for M(III) ions the Δ value is often about 3/2 times the value expected for M(II) ions.

The free ion value of B for a V(III) ion is 860 cm-1 and the reduction of this value noted for the
observed B' is a measure of what is described as the Nephelauxetic Effect.

The Nephelauxetic Effect

The Racah repulsion parameters for a metal complex vary as the ligand is changed

 As the complex becomes more covalent the electrons are to some extent spread over the
ligands so the electron-electron repulsion is reduced
 This reduction in repulsion as covalency increases is called the nephelauxetic effect
(literally "cloud expanding")

A nephelauxetic series can be set up based on the variation of the Racah parameter.
A large reduction in B (free ion) indicates a strong Nephelauxetic Effect.

{B(free ion)- B'(Complex)} / B(free ion)

The Nephelauxetic Series is given by:

F- < H2O < urea < NH3 < en ~ C2O42- < NCS- < Cl- ~ CN- < Br- < S2- ~ I-
This series is consistent with fluoride complexes being the most ionic and giving a small
reduction in B while covalently bonded ligands such as I- give a large reduction of B.

N.B. The order of the nephelauxetic series is NOT the same as the spectrochemical series as
one is an indication of B and the other of Δ

As an example of a Cr(III) complex, using the observed peaks found for [Cr(NH3)6]3+ in Table 1
above, namely ν1 = 21550 cm-1 and ν2 = 28500 cm-1 the ratio of ν2/ν1 = 1.32.
The value of Δ is obtained directly from the first transition so Δ/B' is equal to ν1/B' and finding
B' is now relatively straightforward since from the first transition energy of 21,550 cm-1 and the
value of Δ/B' (ν1/B') of 32.6 we get:
B' = 21,550/ 32.6 or B' = 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).

It is important to remember that for spectra recorded in solution the width of the peaks may be as
large as 1-2000 cm-1 so as long as it is possible to unambiguously assign peaks, the techniques
are valuable.
high-spin octahedral d5 case and low-spin complexes

For Mn(II) and other d5 cases, the ground state is 6S and higher states include, 4G, 4D, 4P 4F etc.
It is expected that since there are NO spin-allowed transitions possible, the electronic spectrum
should only contain very weak bands. For the other electronic configurations spin-forbidden
bands are rarely observed since they are hidden by the more intense spin-allowed transitions.
Since there are now no spin-allowed transitions, by amplifying the signal and using concentrated
solutions, a number of weak peaks can be seen.

The Tanabe-Sugano diagram can be used to interpret these bands by once again calculating the
ratio of the energies of 2 peaks and finding that position on the diagram.
Use of JAVA applets and spreadsheets

To overcome the problem of small diagrams found in textbooks, it was decided to generate our
own Tanabe-Sugano diagrams using spreadsheets. This was done, using the transition energies
given in the Appendix, for the spin-allowed transitions and using CAMMAG to generate the
energies of the spin-forbidden transitions.

Even so, the method of finding the correct X-intercept is somewhat tedious and time-consuming
and a different approach was devised using JAVA applets.
The JAVA applets display the transitions and when the user clicks on any region of the graph
then the values of ν2/ ν1 and ν3/ν1 are displayed. In addition, the values of Δ/B and the Y-
intercepts are given as well. This simplifies the process of determining the best fit for Δ/B.

The expected ranges for the ratio of ν2/ν1 are:

 for d2 (oct) 2.2 - 1.3 for Δ/B 10 - 35

 for d3 (oct) 1.8 - 1.2 for Δ/B 0 - 50
 for d8 (oct) 1.8 - 1.5 for Δ/B 0 - 18
 for d7 (tet) 1.8 - 1.5 for Δ/B 0 - 15

These ratios show the need for a certain degree of precision in attempting to analyse the spectra,
especially for d7 and d8. It has been suggested that instead of using ν2/ ν1 that any two ratios can
be used and graphs of these plots were produced by Lever in the 1960's[11]. Once again though
the published diagrams are rather small and so the spreadsheets above contain these charts which
can be printed in larger scale. The slopes of the various ratio lines vary greatly and it is useful to
examine the region of interest first before deciding on which set of lines should be used for
analysis. If only 2 peaks are observed then this is not an option.

For the spin-allowed diagrams:

 The first applies to d3, d8 (oct) d2, d7 (tet) systems.

 the second applies to d2, d7 (high spin only) (oct), d3, d8 (tet) systems.

A full set of Tanabe-Sugano diagrams that has both the spin-allowed and spin-forbidden energies
are available as well.

Further information for use in laboratory classes is available and some example calculations are
available as well.

References

1. Basic Inorganic Chemistry, F.A.Cotton, G.Wilkinson and P.L.Gaus, 3rd edition, John Wiley
and Sons, Inc. New York, 1995.
2. Physical Inorganic Chemistry, S.F.A.Kettle, Oxford University Press, New York, 1998.
3. Complexes and First-Row Transition Elements, D.Nicholls, Macmillan Press Ltd, London
1971.
4. The Chemistry of the Elements, N.N.Greenwood and A.Earnshaw, Pergamon Press, Oxford,
1984.
5. Concepts and Models of Inorganic Chemistry, B.E.Douglas, D.H.McDaniel and J.J.Alexander
2nd edition, John Wiley & Sons, New York, 1983.
6. Inorganic Chemistry, J.A.Huheey, 3rd edition, Harper & Row, New York, 1983.
7. Inorganic Chemistry, G.L.Meissler and D.A.Tarr, 2nd edition, Prentice Hall, New Jersey,
1998.
8. Inorganic Chemistry, D.F.Shriver and P.W.Atkins, 3rd edition, W.H.Freeman, New York,
1999.
9. Basic Principles of Ligand Field Theory, H.L.Schlafer and G.Gliemann, Wiley-Interscience,
New York, 1969.
10. Y.Tanabe and S.Sugano, J. Phys. Soc. Japan, 9, 1954, 753 and 766.
11(a). Inorganic Electronic Spectroscopy, A.B.P.Lever, 2nd Edition, Elsevier Publishing Co.,
Amsterdam, 1984.
11(b). A.B.P.Lever in Werner Centennial, Adv. in Chem Series, 62, 1967, Chapter 29, 430.
12(a). Introduction to Ligand Fields, B.N.Figgis, Wiley, New York, 1966.
12(b). Ligand Field Theory and Its Applications, B.N. Figgis and M.A. Hitchman, Wiley-VCH:
New York, 2000. ISBN 0-471-31776-4.
13. E.Konig, Structure and Bonding, 9, 1971, 175.
14. Y. Dou, J. Chem. Educ, 67, 1990, 134.

Appendix

Transitions calculated for spin-allowed terms in the Tanabe-Sugano diagrams.

Octahedral d3 (e.g. Chromium(III) ).

4
T2g ← 4A2g , ν1/B= Δ/B
4
T1g(F) ← 4A2g, ν2/B= ½{15 + 3( Δ/B) - √(225 - 18(Δ/B) + ( Δ/B)2 ) }
4
T1g(P) ← 4A2g, ν3/B= ½{15 + 3( Δ/B) + √(225 - 18(Δ/B) + ( Δ/B)2 ) }

from this, the ratio ν2/ν1 would become:

½{15 + 3( Δ/B) - √(225 - 18(Δ/B) + ( Δ/B)2 ) } / Δ/B

and the range of Δ/B required is from ~15 to ~55

Octahedral d8 (e.g. Nickel(II) ).

3
T2g ← 3A2g, ν1/B= Δ/B
3
T1g(F) ← 3A2g, ν2/B= ½{15 + 3(Δ/B) - √(225 - 18(Δ/B) + ( Δ/B)2 ) }
3
T1g(P) ← 3A2g, ν3/B= ½{15 + 3(Δ/B) + √(225 - 18(Δ/B) + ( Δ/B)2 ) }

from this the ratio ν2/ν1 would become:

½{15 + 3( Δ/B) - √(225 - 18(Δ/B) + ( Δ/B)2 ) } / Δ/B

and the range of Δ/B required is from ~5 to ~17

Octahedral d2 (e.g. Vanadium(III) ).

3
T2g ← 3T1g , ν1/B= ½{(Δ/B) - 15 + √(225 + 18(Δ/B) + ( Δ/B)2 ) }
3
T1g(P) ← 3T1g, ν2/B= √(225 + 18(Δ/B) + (Δ/B)2 )
3
A2g ← 3T1g, ν3/B= ½{ 3 (Δ/B) -15 + √(225 + 18(Δ/B) + ( Δ/B)2 ) }

from this the ratio ν2/ν1 would become:

√(225 + 18(Δ/B) + ( Δ/B)2 ) / ½{( Δ/B) - 15 + √(225 + 18(Δ/B) + ( Δ/B)2 ) }

and the range of Δ/B required is from ~15 to ~35

Tetrahedral d7 (e.g. Cobalt(II) ).

4
T2 ← 4A2, ν1/B= Δ/B
4
T1 (F) ← 4A2, ν2/B= ½{15 + 3(Δ/B) - √(225 - 18(Δ/B) + ( Δ/B)2 ) }
4
T1 (P) ← 4A2, ν3/B= ½{15 + 3(Δ/B) + √(225 - 18(Δ/B) + ( Δ/B)2 ) }

from this the ratio ν2/ν1 would become:

½{15 + 3(Δ/B) - √(225 - 18( Δ/B) + ( Δ/B)2 ) } / Δ/B

and the range of Δ/B required is from ~3 to ~8.