What is the Franck-Condon principle?

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SUMMARY

The Franck-Condon principle describes the relationship between electronic transitions and nuclear motion in molecules. It utilizes Fermi's Golden Rule to express the transition probability through the product of electronic and nuclear wavefunctions, specifically represented by the equation r_{i\rightarrow j}=\left\langle \eta_i(R) \varphi_i(r,R) |\mu| \varphi_j(r,R) \eta_j(R) \right\rangle. The principle simplifies the treatment of electronic and nuclear integrals by allowing the electronic integral to be evaluated independently of the nuclear integral. Additionally, the approximation can be enhanced by employing diabatic electronic states, which exhibit minimal dependence on nuclear coordinates.

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  • Understanding of quantum mechanics and wavefunctions
  • Familiarity with Fermi's Golden Rule
  • Knowledge of electronic and nuclear motion in molecular systems
  • Concept of diabatic vs. adiabatic electronic states
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  • Study the derivation and applications of Fermi's Golden Rule
  • Explore the mathematical formulation of the Franck-Condon principle
  • Investigate the differences between diabatic and adiabatic states in quantum chemistry
  • Learn about semiclassical approximations in molecular transitions
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Chemists, physicists, and researchers in quantum mechanics or molecular spectroscopy who seek to understand electronic transitions and their implications in molecular behavior.

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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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From the BO approximation, we have the product of the electronic \varphi_i(r,R) and the nuclear \eta_i(R) wavefunction. For the transition, we use Fermi's Golden rule, where the Dipole-Operator \mu "initiates" the transition. So we end up in
r_{i\rightarrow j}=\left\langle \eta_i(R) \varphi_i(r,R) |\mu| \varphi_j(r,R) \eta_j(R) \right\rangle.
Here we have an inner integral over the electron coordinates r and an outer integral over the nuclei coordinates R. It is important to note here that the inner integral \left\langle \varphi_i(r,R) |\mu| \varphi_j(r,R) \right\rangle is a function of R. The approximation is now that this inner integral is taken out of the outer interal, even though the former one is dependent of R - which is the integration variable of the outer integral. Now the above equation looks like this:
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
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!
 
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.
 

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