Scribd
Upload
121 views4 pages

TS Diagram

The Tanabe-Sugano diagram plots orbital energy as a function of the Racah parameter B and ligand field splitting energy Δo/B. It is used to explain d-d absorption spectra of octahedral complexes and predict absorptions based on ground state transitions. The diagram can be applied to both high and low spin complexes unlike earlier models. For example, analysis of a [V(H2O)]3+ UV spectrum using the diagram estimates the ligand field splitting energy Δo as 2.38 eV or 520 nm.

Uploaded by

sridharR hahaha
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
121 views4 pages

TS Diagram

The Tanabe-Sugano diagram plots orbital energy as a function of the Racah parameter B and ligand field splitting energy Δo/B. It is used to explain d-d absorption spectra of octahedral complexes and predict absorptions based on ground state transitions. The diagram can be applied to both high and low spin complexes unlike earlier models. For example, analysis of a [V(H2O)]3+ UV spectrum using the diagram estimates the ligand field splitting energy Δo as 2.38 eV or 520 nm.

Uploaded by

sridharR hahaha
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

Tanabe-Sugano Diagram

• The Tanabe-Sugano diagram is a plot of orbital energy as a function of the Racah parameter
B vs Δo/B.
• Yukito Tanabe and satoru sugano- On the Absorption spectra of "complex ions"-1954.
• Explain the absorption spectra of octahedral complex ions.
• used in coordination chemistry to predict absorptions in the UV, visible and IR
electromagnetic spectrum of coordination compounds.
• can be used for both high spin and low spin complexes.
• Ground state is taken as constant reference and energies of all other terms are plotted with
respect to ground state.
• In d1 & d9 systems, only one single electron does undergoes transition from T2g to Eg and
vice versa. So there is no electron repulsion and it takes minimum amount of energy.
• In d10 system, there are no d-d electron transitions in d10 metal complexes because the d
orbitals are completely filled. Thus, UV-vis absorption bands are not observed and a
Tanabe–Sugano diagram does not exist.
For example, we take
[V(H2O)]3+ UV spectrum……

Here, V1 = 17794 cm-1, V2 = 25707 cm-1.


Step 1 : Find energy ratio
V2/V1 = 25707/17794 = 1.44

Step 2 : Find o/B by using Sugano diagram


So o/B = 31

V2/V1 = 1.44

31

Step 3 : Determine the Racah parameter(B) using TS diagram


For V2, E/B = 41
V2/B = 41
25707/B = 41
B = 627cm-1
For V1, E/B = 29
V1/B = 29
17794/B = 29
B = 613cm-1

Bavg = 620 cm-1


3
1

Step 4 : Determine o
o /B = 31
o/620 = 31
o = 19229 cm-1
So o = 19229 cm-1 or 2.38eV or 520nm
10Dq = o
10Dq = 2.38
Dq = 0.238 eV
So o = 520nm

For [V(H2O)6]3+
H2O ligand is weak field ligand and have hign spin. So the absorption range is increased from
520nm to 562nm.

Nephelauxetic ratio
For example, [V(H2O)]3+ complex Racah parameter values are B1 = 613cm-1 and B2 = 627cm-1 …
So the Nephalauxetic ratio is …
B1/B2 = 613/627 = 0.978
Hence, inner electronic repulsion has been decreased during the process of complexation.
So the weak field ligand require energy to split the d orbital for electron transfer from the ligand to
metal.

Advantages
• Tanabe-Sugano diagrams can be used for both high spin and low spin complexes, unlike
Orgel diagrams which apply only to high spin complexes.
• In a Tanabe-Sugano diagram, the ground state is used as a constant reference, in contrast
to Orgel diagrams.
• However, if the ligand field splitting energy, 10Dq, is greater than the electron-repulsion
energy, then Orgel diagrams fail in determining electron placement whereas Tanabe-Sugano
diagrams can be applied to situations when 10Dq is significantly greater than electron
repulsion.
Applications
• Shows the energy splitting of the spectral terms with the increase of the ligand field
strength.
• It is even easier to predict the possible transitions and their relative intensity.
• Used to predict the position of electronic transition.
• Tanabe-Sugano diagrams are very useful tools for analyzing UV-vis spectra:
➢ they are used to assign bands.
➢ calculate Dq values for ligand field splitting.

You might also like