What is the Franck-Condon principle?

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In summary: This is done by introducing the Fermi function \phi(r,R):r_{i\rightarrow j}=\left\langle \phi(r,R) |\mu| \phi(r-\Delta r,R) \right\rangle.The semiclassical expression for the transition now becomes:r_{i\rightarrow j}=\left\langle \eta_i(R) \varphi_i(r,R) |\mu| \eta_j(R) \right\rangle.The final step in the Franck-Condon approximation is to replace the Fermi function by the Bose function. This is done
  • #1
physics love
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hi guys

I want to know what is the Franck-Condon principle?... please in details

thanks for all
 
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  • #3
From the BO approximation, we have the product of the electronic [itex]\varphi_i(r,R)[/itex] and the nuclear [itex]\eta_i(R)[/itex] wavefunction. For the transition, we use Fermi's Golden rule, where the Dipole-Operator [itex]\mu[/itex] "initiates" the transition. So we end up in
[itex]r_{i\rightarrow j}=\left\langle \eta_i(R) \varphi_i(r,R) |\mu| \varphi_j(r,R) \eta_j(R) \right\rangle[/itex].
Here we have an inner integral over the electron coordinates [itex]r[/itex] and an outer integral over the nuclei coordinates [itex]R[/itex]. It is important to note here that the inner integral [itex]\left\langle \varphi_i(r,R) |\mu| \varphi_j(r,R) \right\rangle[/itex] is a function of [itex]R[/itex]. The approximation is now that this inner integral is taken out of the outer interal, even though the former one is dependent of [itex]R[/itex] - which is the integration variable of the outer integral. Now the above equation looks like this:
[itex]r_{i\rightarrow j}= \left\langle\varphi_i(r,R) |\mu| \varphi_j(r,R) \right\rangle \cdot\left\langle \eta_i(R)|\eta_j(R) \right\rangle[/itex]
So actually the electronic integral is handled independently of the nuclei integral. The former one is a usual transition (with an operator for the transition according to Fermi's Golden rule), while the latter one is only an overlap of wavefunctions any more!
 
  • #4
Schafspelz, the approximation you made can be justified further by using diabatic electronic states ##\eta_j## instead of the adiabatic electronic wavefunctions. The diabatic states depend only very little on R.
A second step in the Franck-Condon approximation is to replace the dipole integral by a semiclassical expression so that only the neighbourhoods of the turning points of the nuclear motion contribute to the integrand.
 

Related to What is the Franck-Condon principle?

1. What is the Franck-Condon principle?

The Franck-Condon principle is a fundamental concept in spectroscopy that explains the probability of electronic transitions between different energy states of a molecule. It states that during an electronic transition, the nuclei of the molecule remain fixed in their initial positions, with no change in their vibrational or rotational energy levels.

2. Who discovered the Franck-Condon principle?

The Franck-Condon principle was first proposed in 1926 by two German physicists, James Franck and Gustav Hertz. They observed that during an electronic transition in a gas molecule, the energy is absorbed or emitted almost instantaneously, without any significant change in the molecule's nuclear configuration.

3. How does the Franck-Condon principle relate to molecular spectroscopy?

The Franck-Condon principle is essential in understanding the intensity and shape of spectral lines in molecular spectroscopy. It explains why certain electronic transitions are more likely to occur than others, and how the energies of these transitions can be measured to determine molecular structure and properties.

4. Can the Franck-Condon principle be applied to all molecules?

Yes, the Franck-Condon principle is a universal concept that applies to all molecules, regardless of their size or complexity. It is a fundamental principle in quantum mechanics and is used in various fields of chemistry, such as analytical, physical, and organic chemistry.

5. How is the Franck-Condon principle experimentally verified?

The Franck-Condon principle is experimentally verified through spectroscopic techniques such as absorption, emission, and Raman spectroscopy. By measuring the intensity and shape of spectral lines, scientists can determine the probability of electronic transitions and confirm the validity of the Franck-Condon principle.

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