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TanabeSugano diagram

For other uses of T-S diagram, see Temperature exist, A, B, and C, which describe various aspects of inentropy diagram.
terelectronic repulsion. A is an average total interelectron
repulsion. B and C correspond with individual d-electron
TanabeSugano diagrams are used in coordination repulsions. A is constant among d-electron conguration,
and it is not necessary for calculating relative energies,
chemistry to predict absorptions in the UV, visible and IR
electromagnetic spectrum of coordination compounds. hence its absence from Tanabe and Suganos studies of
complex ions. C is necessary only in certain cases. B is
The results from a TanabeSugano diagram analysis of
[5]
a metal complex can also be compared to experimental the most important of Racahs parameters in this case.
spectroscopic data. They are qualitatively useful and can One line corresponds to each electronic state. The bendbe used to approximate the value of 10Dq, the ligand ing of certain lines is due to the mixing of terms with
eld splitting energy. TanabeSugano diagrams can be the same symmetry. Although electronic transitions are
used for both high spin and low spin complexes, unlike only allowed if the spin multiplicity remains the same
Orgel diagrams, which apply only to high spin complexes. (i.e. electrons do not change from spin up to spin down
TanabeSugano diagrams can also be used to predict the or vice versa when moving from one energy level to ansize of the ligand eld necessary to cause high-spin to low- other), energy levels for spin-forbidden electronic states
are included in the diagrams, which are also not included
spin transitions.
in Orgel diagrams.[6] Each state is given its symmetry laIn a TanabeSugano diagram, the ground state is used as bel (e.g. A , T , etc.), but g and u subscripts are
a constant reference, in contrast to Orgel diagrams. The usually left o because it is understood that all the states
energy of the ground state is taken to be zero for all eld are gerade. Labels for each state are usually written on
strengths, and the energies of all other terms and their the right side of the table, though for more complicated
components are plotted with respect to the ground term. diagrams (e.g. d6 ) labels may be written in other locations for clarity. Term symbols (e.g. 3 P, 1 S, etc.) for a
specic dn free ion are listed, in order of increasing energy, on the y-axis of the diagram. The relative order of
1 Background
energies is determined using Hunds rules. For an octahedral complex, the spherical, free ion term symbols split
Until Yukito Tanabe and Satoru Sugano published their accordingly:[7]
paper On the absorption spectra of complex ions, little
4
5
6
7
was known about the excited electronic states of complex Certain TanabeSugano diagrams (d , d , d , and d )
metal ions. They used Hans Bethe's crystal eld theory also have a vertical line drawn at a specic Dq/B value,
and Giulio Racah's linear combinations of Slater inte- which corresponds with a discontinuity in the slopes of
grals,[1] now called Racah parameters, to explain the ab- the excited states energy levels. This pucker in the lines
sorption spectra of octahedral complex ions in a more occurs when the spin pairing energy, P, is equal to the
quantitative way than had been achieved previously.[2] ligand eld splitting energy, Dq. Complexes to the left of
Many spectroscopic experiments later, they estimated the this line (lower Dq/B values) are high-spin, while comvalues for two of Racahs parameters, B and C, for each plexes to the right (higher Dq/B values) are low-spin.
2
3
d-electron conguration based on the trends in the ab- There is no low-spin or high-spin designation for d , d ,
8 [8]
sorption spectra of isoelectronic rst-row transition met- or d .
als. The plots of the energies calculated for the electronic
states of each electron conguration are now known as
3 Tanabe-Sugano diagrams
TanabeSugano diagrams.[3][4]

The seven TanabeSugano diagrams for octahedral complexes are shown below.[5][9][10]

Parameters

The x-axis of a TanabeSugano diagram is expressed in


terms of the ligand eld splitting parameter, Dq, or , divided by the Racah parameter B. The y-axis is in terms
of energy, E, also scaled by B. Three Racah parameters

4 Unnecessary diagrams: d1 , d9
and d10
1

4.1

7 APPLICATIONS AS A QUALITATIVE TOOL

d1

There is no electron repulsion in a d1 complex, and the


single electron resides in the t orbital ground state. A d1
octahedral metal complex, such as [Ti(H2 O)6 ]3+ , shows
a single absorption band in a UV-vis experiment.[5] The
term symbol for d1 is 2 D, which splits into the 2 T and
2
E states. The t orbital set holds the single electron
and has a 2 T state energy of 4Dq. When that electron is promoted to an e orbital, it is excited to the 2 E
state energy, +6Dq. This is in accordance with the single
absorption band in a UV-vis experiment. The prominent
shoulder in this absorption band is due to a Jahn-Teller
distortion which removes the degeneracy of the two 2 E
states. However, since these two transitions overlap in a
UV-vis spectrum, this transition from 2 T to 2 E does
not require a TanabeSugano diagram.

4.2

d9

Similar to d1 metal complexes, d9 octahedral metal complexes have 2 D spectral term. The transition is from the
(t )6 (e )3 conguration (2 E state) to the (t )5 (e )4 conguration (2 T state). This could also be described as a
positive hole that moves from the e to the t orbital
set. The sign of Dq is opposite that for d1 , with a 2 E
ground state and a 2 T excited state. Like the d1 case, d9
octahedral complexes do not require the TanabeSugano
diagram to predict their absorption spectra.

6 Advantages over Orgel diagrams


In Orgel diagrams, the magnitude of the splitting energy
exerted by the ligands on d orbitals, as a free ion approach
a ligand eld, is compared to the electron-repulsion energy, which are both sucient at providing the placement
of electrons. However, if the ligand eld splitting energy,
10Dq, is greater than the electron-repulsion energy, then
Orgel diagrams fail in determining electron placement. In
this case, Orgel diagrams are restricted to only high spin
complexes.[6]
TanabeSugano diagrams do not have this restriction, and
can be applied to situations when 10Dq is signicantly
greater than electron repulsion. Thus, TanabeSugano
diagrams are utilized in determining electron placements
for high spin and low spin metal complexes. However,
they are limited in that they have only qualitative significance. Even so, TanabeSugano diagrams are useful in
interpreting UV-vis spectra and determining the value of
10Dq.[6]

7 Applications as a qualitative tool


In a centrosymmetric ligand eld, such as in octahedral
complexes of transition metals, the arrangement of electrons in the d-orbital is not only limited by electron repulsion energy, but it is also related to the splitting of the
orbitals due to the ligand eld. This leads to many more
electron conguration states than is the case for the free
ion. The relative energy of the repulsion energy and splitting energy denes the high-spin and low-spin states.

Considering both weak and strong ligand elds, a


TanabeSugano diagram shows the energy splitting of
the spectral terms with the increase of the ligand eld
There are no d-d electron transitions in d10 metal com- strength. It is possible for us to understand how the enplexes because the d orbitals are completely lled. Thus, ergy of the dierent conguration states is distributed at
UV-vis absorption bands are not observed and a Tanabe certain ligand strengths. The restriction of the spin selection rule makes it is even easier to predict the posSugano diagram does not exist.
sible transitions and their relative intensity. Although
they are qualitative, TanabeSugano diagrams are very
useful tools for analyzing UV-vis spectra: they are used
to assign bands and calculate Dq values for ligand eld
5 Diagrams for tetrahedral sym- splitting.[11][12]

4.3

d10

metry
7.1 Examples
Tetrahedral TanabeSugano diagrams are generally not
found in textbooks because the diagram for a dn tetrahedral will be similar to that for d(10-n) octahedral, remembering that T for tetrahedral complexes is approximately
4/9 of O for an octahedral complex. A consequence of
the much smaller size of T results in (almost) all tetrahedral complexes being high spin and therefore the change
in the ground state term seen on the X-axis for octahedral
d4 -d7 diagrams is not required for interpreting spectra of
tetrahedral complexes.

7.1.1 Manganese(II) hexahydrate


In the [Mn(H2 O)6 ]2+ metal complex, manganese has an
oxidation state of +2, thus it is a d5 ion. H2 O is a weak
eld ligand (spectrum shown below), and according to the
TanabeSugano diagram for d5 ions, the ground state is
6
A1 . Note that there is no sextet spin multiplicity in any
excited state, hence the transitions from this ground state
are expected to be spin-forbidden and the band intensities

7.2

Solving for B and O

3
shoulder) is predicted to be 4 T1 to 4 A2 . The small energy
dierence leads to the overlap of the two peaks, which
explains the broad peak observed in the visible spectrum.

7.2 Solving for B and O

Absorption spectrum of [Mn(H2 O)6 ]2+ .

should be low. From the spectra, only very low intensity


bands are observed (low Molar absorptivity () values on
y-axis).[11]

d2 Tanabe-Sugano diagram

Absorption spectrum of [Co(H2 O)6 ]2+ .

7.1.2

Cobalt(II) hexahydrate

Another example is [Co(H2 O)6 ]2+ .[12] Note that the ligand is the same as the last example. Here the cobalt ion
has the oxidation state of +2, and it is a d7 ion. From the
high-spin (left) side of the d7 TanabeSugano diagram,
the ground state is 4 T1 (F), and the spin multiplicity is a
quartet. The diagram shows that there are three quartet
excited states: 4 T2 , 4 A2 , and 4 T1 (P). From the diagram
one can predict that there are three spin-allowed transitions. However, the spectra of [Co(H2 O)6 ]2+ does not
show three distinct peaks that correspond to the three predicted excited states. Instead, the spectrum has a broad
peak (spectrum shown below). Based on the T-S diagram, the lowest energy transition is 4 T1 to 4 T2 , which
is seen in the near IR and is not observed in the visible
spectrum. The main peak is the energy transition 4 T1 (F)
to 4 T1 (P), and the slightly higher energy transition (the

For the d2 complex [V(H2 O)6 ]3+ , two bands are observed with maxima at around 17,500 and 26,000 cm1 .
The ratio of experimental band energies is E(2 )/E(1 )
is 1.49. There are three possible transitions expected,
which include: 1 : 3 T 3 T , 2 :3 T 3 T (P), and 3 :
3
T 3 A . There are three possible transitions, but only
two are observed, so the unobserved transition must be
determined.
Fill in a chart like the one to the right by nding corresponding heights (E/B) of the symmetry states at certain values of O / B. Then nd the ratio of these values (E(2 )/E(1 ) and E(3 )/E(1 )). Note that the ratio of E(3 )/E(1 ) does not contain the calculated ratio
for the experimental band energy, so we can determine
that the 3 T 3 A band is unobserved. Use ratios for
E(2 )/E(1 ) and the values of O / B to plot a line with
E(2 )/E(1 ) being the y-values and O/B being the xvalues. Using this line, it is possible to determine the
value of O / B for the experimental ratio. (O / B =
31 for a chart ratio of 1.49 in this example).
Find on the T-S diagram where O / B = 31 for
3
T 3 T and 3 T 3 T (P). For 3 T , E(1 ) / B = 27
and for 3 T (P), E(2 ) / B = 43.
The Racah parameter can be found by calculating B from

both E(2 ) and E(1 ). For 3 T (P), B = 26,000 cm1 /43


= 604 cm1 . For 3 T , B = 17,500 cm1 / 27 = 648 cm1 .
From the average value of the Racah parameter, the ligand eld splitting parameter can be found (O). If O /
B = 31 and B = 625 cm1 , then O = 19,375 cm1 .

See also
Character tables
Crystal eld theory
d electron count
Hans Bethe
Laporte rule
Ligand eld theory
Molecular symmetry
Orgel diagram
Racah parameter
Spin states (d electrons)
Term symbol

References

[1] Racah, Giulio (1942).


Theory of complex spectra II.
Physical Review 62 (9
10):
438462.
Bibcode:1942PhRv...62..438R.
doi:10.1103/PhysRev.62.438.
[2] Tanabe, Yukito; Sugano, Satoru (1954). On the absorption spectra of complex ions I. Journal of the Physical Society of Japan 9 (5): 753766. doi:10.1143/JPSJ.9.753.
[3] Tanabe, Yukito; Sugano, Satoru (1954). On the
absorption spectra of complex ions II.
Journal
of the Physical Society of Japan 9 (5): 766779.
doi:10.1143/JPSJ.9.766.
[4] Tanabe, Yukito; Sugano, Satoru (1956). On the
absorption spectra of complex ions III.
Journal
of the Physical Society of Japan 11 (8): 864877.
doi:10.1143/JPSJ.11.864.
[5] Atkins, Peter; Overton, Tina; Rourke, Jonathan; Weller,
Mark; Armstrong, Fraser; Salvador, Paul; Hagerman,
Michael; Spiro, Thomas; Stiefel, Edward (2006). Shriver
& Atkins Inorganic Chemistry (4th ed.). New York: W.H.
Freeman and Company. pp. 478483. ISBN 0-71674878-9.
[6] Douglas, Bodie; McDaniel, Darl; Alexander, John (1994).
Concepts and Models of Inorganic Chemistry (3rd ed.).
New York: John Wiley & Sons. pp. 442458. ISBN
0-471-62978-2.

REFERENCES

[7] Cotton, F. Albert; Wilkinson, Georey; Gaus, Paul L.


(1995). Basic Inorganic Chemistry (3rd ed.). New York:
John Wiley & Sons. pp. 530537. ISBN 0-471-50532-3.
[8] Harris, Daniel C.; Bertolucci, Michael D. (1978). Symmetry and Spectroscopy: An Introduction to Vibrational and
Electronic Spectroscopy. New York: Dover Publications,
Inc. pp. 403409, 539. ISBN 978-0-486-66144-5.
[9] Lancashire, Robert John (410 June 1999), Interpretation
of the spectra of rst-row transition metal complexes
(PDF), CONFCHEM, ACS Division of Chemical Education
[10] Lancashire, Robert John (25 September 2006). TanabeSugano diagrams via spreadsheets. Retrieved 29 November 2009.
[11] Jrgensen, Chr Klixbll; De Verdier, Carl-Henric; Glomset, John; Srensen, Nils Andreas (1954). Studies of absorption spectra IV: Some new transition group bands of
low intensity. Acta Chem. Scand. 8 (9): 15021512.
doi:10.3891/acta.chem.scand.08-1502.
[12] Jrgensen, Chr Klixbll; De Verdier, Carl-Henric; Glomset, John; Srensen, Nils Andreas (1954). Studies of
absorption spectra III: Absoprtion Bands as Gaussian Error Curves. Acta Chem. Scand. 8 (9): 14951501.
doi:10.3891/acta.chem.scand.08-1495.

10
10.1

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