[Physics] Why absorption spectum is not identical to emission spectrum

photon-emissionspectroscopy

Hydrogen emission and absorption spectral lines are typically depicted as the same:

enter image description here(source)

However, in more complex systems, the emission and absorption spectra are significantly different. For example:

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Absorption and photoluminescence spectra of DCJTB doped in a PS film.
(source)

What causes this shift of $\lambda_{\text{max}}$ etc. between absorption and emission?

Best Answer

As @MikaelKuisma mentioned, the reason for this difference is the contribution of nuclear vibrational overlap to the transition moment. When an electron is excited from a ground state $S_0$ to the first excited state $S_1$, the bond is stretched and the internuclear separation increases:

enter image description here (source: Martin Pope and Charles E. Swenberg, Electronic Processes in Organic Crystals and Polymers, 1999)

Assuming harmonic oscillations, the overlap between each two vibrational wavefunctions (different energy level for different frequencies/number of nodes) is defined as the nuclear vibrational overlap, which in turn contributes to the total transition moment.

The intensity of absorption/emission is proportional to the transition moment squared, $d_{nm}^2$ (following Beer-Lambert's law):

$$I = I_0 10^{-\varepsilon c l}$$ $$A = \log \frac{I_0}{I} = \varepsilon c l \propto d_{nm}^2$$

which means that factors contributing to the transition moment are expressed in the absorption/emission spectra.

For more information see Franck-Condon principle.

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