What is the Franck-Condon principle?

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Discussion Overview

The discussion centers around the Franck-Condon principle, exploring its theoretical foundations, mathematical formulations, and implications in the context of molecular transitions. Participants seek detailed explanations and engage with the principle's application in quantum mechanics.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant requests a detailed explanation of the Franck-Condon principle.
  • Another participant provides a link to a Wikipedia article for reference.
  • A participant discusses the Born-Oppenheimer approximation and the mathematical formulation of transitions using Fermi's Golden rule, emphasizing the separation of electronic and nuclear wavefunctions.
  • Further elaboration includes the treatment of integrals over electronic and nuclear coordinates, noting the dependency of the inner integral on the outer integral's variable.
  • Another participant suggests justifying the approximation using diabatic electronic states, which are less dependent on nuclear coordinates, and mentions a semiclassical approach to the dipole integral that focuses on nuclear motion turning points.

Areas of Agreement / Disagreement

Participants present various perspectives on the Franck-Condon principle, with some agreeing on the mathematical treatment while others propose alternative approaches. The discussion remains unresolved regarding the best methods to apply the principle and the implications of different approximations.

Contextual Notes

The discussion includes assumptions about the applicability of the Born-Oppenheimer approximation and the treatment of wavefunctions, which may not be universally accepted. The mathematical steps and justifications for approximations are not fully resolved.

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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 [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!
 
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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