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For equal-frequency harmonic ground and excited molecular potentials displaced by $\Delta Q$, the low-temperature vibrational overlap has the Poisson weights in the title, with $S=M{\omega }_v(\Delta Q{)}^2/(2\hslash )$. Optical lines occur at $E_{00}+\nu \hslash {\omega }_v$, apart from broadening and slowly varying electronic or optical prefactors. The normalized weights sum to one and have mean vibrational excitation $S$. Unequal frequencies, several vibrations, hot initial states and intermolecular coupling modify this simple Franck-Condon principle model.

An organic semiconductor has conjugated molecular units with strong intramolecular bonding and comparatively weak intermolecular electronic overlap. Optical excitation commonly promotes a $\pi$ electron from an occupied molecular orbital toward an unoccupied one. Weak dielectric screening and narrow bands favour bound Frenkel excitons, sometimes mixed with intermolecular charge-transfer states, rather than immediate production of free carriers. The optical excitation energy is below the unbound electron–hole threshold by the exciton binding energy, with relaxation conventions specified when comparing measured gaps.

The electric-dipole interaction selects bright states through their transition dipoles, producing polarization-dependent absorption in oriented samples. From a singlet ground state, strong electric-dipole absorption normally preserves spin and reaches singlet excitons; direct triplet excitation is weak without spin mixing. The Franck-Condon principle treats excitation as vertical on the nuclear-motion timescale. For one displaced harmonic vibration at low temperature, the displaced-oscillator Franck-Condon progression has relative strengthsHere the Huang-Rhys factor $S$ measures the displacement and $E_{00}$ is the zero-vibration transition energy. Vibrational relaxation before emission produces a Stokes shift. Molecular packing and excitonic coupling shift or split bright features and change their intensities; disorder and vibrations broaden them. Consequently a universal parabolic-band absorption edge is inappropriate for a localized molecular excitation.^[ref]

The approximate mirror relationship follows from the Franck-Condon principle when the ground and excited electronic states have similar vibrational frequencies and comparable potential shapes displaced along the active coordinates. Absorption samples $S_0,v\simeq 0\to S_1,v^{\prime }$ overlaps, while relaxed emission samples $S_1,v^{\prime }\simeq 0\to S_0,v$ overlaps. For displaced harmonic potentials, the corresponding overlap intensities form similar progressions on opposite sides of the transition between the lowest vibrational levels of the two electronic states.

The symmetry is approximate and is most naturally compared on an energy or wavenumber axis. A wavelength axis is nonlinear in photon energy, and solvent response, frequency changes, differing transition strengths and instrumental corrections can spoil an exact mirror image.