Electronic Spectra of

Transition Metal Complexes

Color

• Color is due to absorption of visible light. Light absorption

causes electronic transition from ground state to excited state.
For absorption to occur, the energy separation between the
ground & excited states (ΔE), must match the frequency (v) of
light. ΔE = hv.
• Color observed is the complementary of color absorbed. For
example, red is complementary to blue; so if red is absorbed,
the color seen is blue. CuSO4 solution is blue as it absorbs red
color.
Transition metal ions & their complexes are variedly colored.
Some sample colors are:
Types of absorption spectra of complexes

• A plot of absorbance, A against wavelength, λ gives absorption spectra.

• Types of absorption spectra of complexes:
• 1. d- d spectra or ligand field spectra
• 2. Charge Transfer (CT) spectra
• 3. Ligand spectra where ligand also absorbs visible light
• 4. Counter- ion spectra where counter ions like NO3- also absorb visible
light.
d- d spectra or ligand field spectra

• d- d spectra or ligand field spectra:

• Ligands split the d-orbitals into sets of different energy. For

example: In ML6 complexes, d-orbitals split into lower energy
set t2g & higher energy eg set.
• d- electron transition occurs from t2g to eg if ΔE = hv. The
absorbed light is visible radiation, the complex appears colored.
Color and ligands
Band spectra

• Electronic spectra - Due to Electronic Transition from ground ( low energy)

state to excited state (higher energy level). A plot of A vs λ gives Electronic
spectra or absorption spectra.
• Each Electronic Transition gives a band in the spectra.
• Absorption spectra of complexes is band spectra.
• Diagram : Absorption spectra of Ti(H2O)6 3+ ion: single broad band.
Absorption Band widths
• d- d spectra is band spectra & not line spectra. The band widths are up to
nearly 1000 cm-1 as in [Ti(H2O)6 3+] ion.
• This is due to
• 1. Non-rigid structure of complexes. Since the structure is
non-rigid, the M- L bond vibrations produce many structures
of slightly different energy; so many transitions with slightly
differences in energy occur. Since, each transition gives a line,
a group of closely spaced lines or a band appears in the spectra.
• 2. Ligand-solvent interaction in solutions also causes band
broadening.
• 3. Spin- orbit coupling widens bands.
• 4. Distortions in regular geometry of molecules like Jahn –
Teller distortions cause band broadening.
Number of bands & Excited states
• Number of bands correspond to number of excited states in the
ion or molecule.
• Thus, for Ti(H2O)6 3+ ion, d1 ion, single broad band due to
(t2g)1 (eg)1 transition - single excited state
• For Cu(H2O)6 2+ ion, d9 ion - single band
• (t2g)6 (eg)3 (t2g)5 (eg)4 ;
Many excited states: electrostatic interactions

• For oct – V(III) ion, d2; Cr(III) ion, d3; Co(II) ion, d7 ; Ni(II)
ion, d8 etc more than One band are observed.
• This indicates more excited states in the configuration of free
ions & complexes.
• The inter electron interactions in multi electron systems is
responsible for the existence of many states within a
configuration (electronic arrangement).
• For example 2p2 configuration.
• The 2 electrons may occupy any of the three p orbitals (l =1).
The ml values for p orbitals are: +1, 0 & -1. It means that there
are three different orientations of their angular momenta.
• Also the spin orientations , ms = +½ or -½ are different.
• Many combinations of ml & ms are possible.
• In other words, there are different ways( i.e.combinations of ms & ml)
in which electrons can occupy the orbitals in a configuration.
• The different ways ( combinations of ms & ml) in which the electrons
can occupy the orbitals in a configuration are called the microstates.
• For example, one microstate for 2p2 configuration is (1+, 1-); this
notation indicates that both the electrons occupy an orbital with
ml=+1 but with opposite spins, the superscript + indicating ms= +½
and – indicating ms= -½ .
• All microstates in a configuration do not have the same energy.
• Microstates having same energy are called terms.
• Terms are represented by 2S + 1 L where 2S + 1 is spin multiplicity; L
is given by L=l1+l2, l1+l2-1…..|l1-l2| .
• Term symbol: each value of L gives term symbol.
• L value: 0 1 2 3 4 5……
• Term symbol: S P D F G H …..
Russell-Saunders coupling scheme
• For light atoms, Russell-Saunders coupling scheme is used to obtain
the terms.
• According to this scheme:
• 1. The spin angular moments of individual electrons, ‘s’ couple
(vectorial addition) to give the total, S ; S = s1 + s2 , s1 + s2 -1, s1 + s2
-2 …. | s1 - s2 |

• For two electrons with s1= ½ & s2= ½,

• S = ½+½, ½+½ -1, ….. | ½ -½ | = 1 (parallel), 0 (paired).

• 2. The orbital angular moments of individual electrons, ‘l’

couple to give the total, L; L= l1+l2, l1+l2-1,….|l1-l2|
• Thus, for d2 configuration, l1=2, l2=2,
• L= 2+2, 2+2-1, ….|2-2| = 4,3,2,1,0
• The s, s and l, l interactions produce terms represented by L.
2S+1

• The values of L correspond to term symbol.

• L value: 0 1 2 3 4 5……
• Term symbol: S P D F G H …..

• 3. The L and S then couple to give the resultant angular momentum

J,
• J = (L+S), (L+S-1), (L+S-2 )…..|L-S|.
• The L – S coupling produces ‘states’ or ‘spectroscopic states’.

• Spectroscopic state is represented by 2S+1LJ.

• In the Term representation 2S+1L, the 2S+1 is called spin multiplicity.
• For p2 configuration, l1=1, l2=1, s1=+1/2, s2=+1/2,
• L=2,1,0, S=1, 0, 2S+1= 3 & 1

• The terms 2S+1L are = 3D, 3P, 3S, - triplets; triplet dee, triplet pee…
• And 1D, 1P, 1S- singlets.- singlert dee, singlet pee….

• Spectroscopic states 2S+1LJ. for the p2 configuration are:

• l1=1, l2=1, s1=+1/2, s2=+1/2,
• L=2,1,0, S=1, 0, 2S+1= 3 & 1;
• J= 3, 2, 1, 0,
Lowest energy term – Ground state term.

• Lowest energy term for the configuration.

• 1. Term with higher spin multiplicity, 2S+1 is ground state term
(lowest energy); more the number of electrons with parallel
spins, lower the energy, more stability, (P.E.P).

• 2. If more terms with same 2S+1 , then, the term with higher L
value is lower energy term.

• 3. In case of same 2S+1 & L, then:

• Term with higher J for more than half-filled orbitals & Term
with smaller J for less than half-filled orbitals is ground state
term.
Deduction of ground state terms

• 1. Using box diagram, the valence electrons are

placed in the decreasing order of ml value and
following P.E.P. ( maximizing spins).
• Then Russell- Saunder’s scheme is applied.
• 2. Then, the total S; S = ∑ s , is computed
• 3. From the value of S spin multiplicity, 2s + 1,
obtained.
• 4. Then total L; L = ∑ ml , is obtained from ml
values.
• 5. Based on L, term symbol & then terms, 2s+1 L, are
assigned.
Deduction of ground state terms…..
• Example: d2 configuration: The 2 electrons are placed in the
orbitals with parallel spins (see box diagram below);
• Then, L= ∑ ml = 2+1= 3, and S = 1/2+1/2 = 1;
2S+1= 3;
• For L=3, term symbol is F & hence ground term is 3F.

Similarly, for d3 configuration, the ground term is : 4F

Ground state terms for d1,d9, d2 & d8 ions
Ground state terms for d4,d6, d3, d7 & d5 ions
Ground state & Excited terms

Confign. Example Number of No. of Ground. Excited terms

microstates terms state term

d 1 & d9 Ti3+, Cu2+ 10 1 2

D -- -- --- -- -

d2 & d8 V3+, Ni2+ 45 5 3

F 3
P, 1
G, 1D, 1S

d3 & d7 Cr3+, Co2+ 120 8 4

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

d4 & d6 Cr2+ , Fe2+ 210 16 5

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

d5 Mn2+ 252 16 6
S 4
G, 4F, 4D, 4P, 2P,

d2 & d8 and d3& d7 have F ground terms, & P first exited states.
Effect of Russell- Saunders coupling on d2 configuration.
Oct. Mn(II) complexes, MnL6.

• Mn2+ is d5 ion, with ground state 6S ;

• There is no exited state with spin multiplicity, 6.
• They are g g transitions
• So d – d transitions in oct. Mn(II) complexes are both spin &
Laporte forbidden.
• Hence, they are extremely less intense & MnL6 complexes
are almost colorless.

• However, MnL4 tetrahedral complexes are intensely colored

since Laporte rule is not applicable to them. Tetrtahedral
complexes do not have centre of symmetry. So the d- orbitals
do not have ‘g’ or ‘u’ character; they are denoted by ‘t2’ & ‘e’.
Orgel diagrams

• These are energy level diagrams.

• Show the variation of energy of terms, E with field strength,
Δ
• Obtained by plotting E vs field strength, Δ
• Only weak fields (h. s) & ground state term is considered.
• Example: For d1 ion, ground term is 2D, splits into 2T2g & 2Eg in
oct. field. So the Orgel diagram is as under:
Orgel diagram of d2 ions

• For d2 ion, ground term is 3F; splits into 3T1g , 3T2g & 3A2g , in
oct. field. 3P is close to 3F; 3P does not split but gives 3T1g state
in oct. field. So the Orgel diagram is as under:
General Orgel Diagram for ‘D’ terms

• d1, d6 tet. & d1, d6 oct. &

• d4, d9 oct. d4, d9 tet.
General Orgel Diagram for ‘F’ terms

• d2, d7 tet. &        d2, d7 oct. &

• d3, d8 oct. d3, d8 tet.
Applications of Orgel diagrams:
• Applications:
• Useful in the interpretation of absorption spectra of complexes.
• Useful to obtain values of Δ , B (Racah Parameter).
• Interpretation of Spectra:
• To predict the number of bands & assignment of the bands
• Orgel diagrams can be used to predict the number of bands
expected in the spectra of a complex & these bands can be
assigned to the corresponding electronic transitions.
• Example: [Ti(H2O)6]3+ .
Spectra of [Ti(H2O)6]3+ ……..
• The ground term is 2T2g & excited term is 2Eg .
• So, Orgel diagram predicts one band due to the transition:

• Absorption spectra of oct. d1 complexes, for example,

[Ti(H2O)6]3+ in aq. solution shows only one band (weak)
around 20,300 cm -1. Thus, the prediction from Orgel diagram
has been correct.
• Calculation of crystal field parameter, Δ:
• The energy difference between the ground & excited terms
gives C. F. splitting Δ, for oct. d1 complexes ; hence for
[Ti(H2O)6]3+ , Δ = 20,300 cm -1.
Orgel diagram & Absorptions spectra of oct. d2 ions
Orgel diagram of d2 ions…….

• Three transitions are possible from the ground term 3T1g :

• 3T1g ---------- 3T2g …… v1 = 8Dq
• 3T1g -------- 3A2g………. v2 = 18Dq
• 3T1g ------- 3T1g(P) ….. v3 = 6Dq + 15B

• So, Orgel diagram for oct. d2 complexes predicts Three

bands.
• But for ligands stronger than water, the 3A2g & 3T1g(P) terms
cross. ( see diagram). 3A2g is very higher energy state.
• So only two bands corresponding to: 3T1g ---- 3T2g &
3
T1g ----- 3T1g(P) are observed.
Absorption spectra of [V(H2O)6]3+

• Example:
• [V(H2O)6]3+ , shows two bands (weak) at 17,250 cm-1 & 25,000 cm-1.
• V3+ is d2 ion. Ground term: 3F& 3P is excited state close to 3P.
• V3+ higher charge, stronger field & only two bands observed (Orgel diagram) since
3
A2g is high energy term.

• Band at 17,250 cm-1 is due to: 3T1g ---------- 3T2g …v1 = 8Dq
• & 25,000 cm-1 is due to:3T1g ---- 3T1g(P) … v3 = 6Dq + 15B.

• From the bands, the C. F. parameters: Δ & B can be calculated.

• 3T1g ---- 3T2g …v1 = 8Dq = 17,250 & Dq = 2156.25; Δ = 10Dq , so Δ =2156.25
x 10 = 21562.5 cm-1 .
• 3T1g ---- 3T1g(P) … v3 = 6Dq + 15B = 25000,

• So, 6Dq + 15B = 25000 & B = 804.13 cm-1 .

• The bands are weak because they are Laporte forbidden.
Absorption spectra of [V(H2O)6]3+
Orgel diagram for d8 ion
• Orgel diagram precits 3 bands for d8 in oct. field due to the transitions:
• 3A2g to 3T2g ; 3A2g to 3T1g(F); 3A2g to 3T1g(P).
• The terms 3T1g(F) & 3T1g(P) bend since like terms do not cross.
Absorption spectra of [Ni(H2O)6]2+ ion

• The green colored aq. solution of [Ni(H2O)6]2+ exhibits three bands around
8,500, 13,800 & 25,300cm-1. Interpret the spectra & calculate , Δ, B &
bending parameter, x.
• 1. Lowest energy transition: 3A2g to 3T2g ; v1= 10Dq = 8, 500 ; Dq = 850
• 2. Next transition 3A2g to 3T1g(F ; v2 = 13,800 = 18Dq – x; x = 1500
• 3. Next transition: 3A2g to 3T1g(P) ; v3 = 25,300 = 15B + 12Dq + x;
• 25,300 = 15B + 10,200 + 1500 ; B = 906.6cm-1.
Absorption spectra of [Cr(H2O)6]3+ion: d3 ion

• For d3 ion ground term is 4F;in oct. field splits as shown below.
• 3 transitions & so 3 bands expected (Orgel diagram)
Absorption spectra of [Cr(H2O)6]3+ion: d3 ion….

• The absorption (Electronic) spectrum of [Cr(H2O)6]3+ in solution

shows three bands:
• v1 = 17,400 cm-1, v2 = 24,500 cm-1, v3 = 37,800 cm-1. Assign the
bands & calculate Δ & B.
• Bands are due to the following transitions (from Orgel diagram):
• v = 4A2g to 4T2g = 17,400
1

• v2 = 4A2g to 4T1g(F) =24, 500

• v3 = 4A2g to 4T1g(P) = 37,800
• v1 = 17,400 = Δ = 10Dq
• v2 = 18Dq – x
• V3 = 15B +12Dq + x
• From Dq value, x & B calculated
Orgel diagram for d7 ion in Oct. field

• For d7 ion, ground term is 4F; splitting pattern is inverse to that

of d3 ion.
• 3 transitions & 3 bands expected
• v1 = 4T1g to 4T2g (F)
• v2 = 4T1g to 4A2g (F)
• v3 = 4T1g to 4T1g (P)
• Spectrum of [Co(H2O)6]2+ ion
shows three bands as expected
from Orgel diagram.
• Absorptions are Laporte forbidden,
so weak.
Absorption spectra of [Co(H2O)6]2+ion: d7 ion….

• The absorption spectra of [Co(H2O)6]2+ion shows three weak absorption

bands at 8,000 cm-1, (ε = 1.3), 19,600 cm-1 (ε =4.8), & 21,600 cm-1 (ε
= 2.1). Interpret the spectra & calculate Δ & B.
• From Orgel diagram for d7 ion in oct, field, the bands are assigned to the
following transitions:
• 8,000 cm-1 = v1 : 4T1g to 4T2g (F)
• 19,600 cm-1 = v2 : 4
T1g to 4A2g (F)
• 21,600 cm-1 = v3 : 4T1g to 4T1g (P)
Limitations of Orgel diagrams

• 1.Applicable only to weak field (h.s.) complexes; with strong

field complexes, spin pairing occurs & with this ground states
change.
• 2.Only low energy ground states are considered; excited states
ignored.
• 3.Energies of terms (& also C.F. states) are influenced not only
by Δ, but also by Racah parameters, B & C. These are ignored
in Orgel diagrams.
• 4.Values of crystal field parameters, Δ & B are only rough
estimates (approximate) due to the above simplifications.