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An exciton is a bound state of an electron and an electron hole. Their opposite electric charges attract through the Coulomb potential, producing a neutral quasiparticle with internal relative motion and motion of its center of mass. In a semiconductor, promoting an electron from the valence band into the conduction band leaves an electron hole; the pair can occupy either an exciton bound state or an unbound scattering state. Merely creating the two charge carriers does not establish binding. A neutral exciton can transport excitation energy without transporting net electric charge. Coupling this material excitation strongly to a photon can form a polariton.

The striking optical consequence is that an exciton optical transition can absorb a photon with less energy than the threshold for creating unbound electrons and electron holes. The difference is the exciton binding energy, not an extra one-electron energy band inside the band gap. The Wannier-Mott exciton supplies a useful large-radius model; the Frenkel exciton describes the opposite, tightly localized limit.^[ref]

A Frenkel exciton is an exciton whose internal excitation is concentrated on the scale of one molecule or unit cell. The local excitation can transfer between sites; localized internal structure does not require an immobile center of mass. The large-radius Wannier-Mott exciton approximation cannot simply be extrapolated to this limit.^[ref]

Molecular excitations in organic semiconductors often retain strong local character. Weak screening supports Frenkel excitons or intermolecular charge-transfer admixtures, so a photon can create a bound neutral excitation rather than free carriers. Transition dipoles, spin selection rules, molecular packing and Franck-Condon factors set the bright spectral features. Disorder and thermal vibrations broaden them. Electronic overlap can also produce more delocalized excitons; the molecular limit is a useful model, not a definition covering every organic solid.

MIT's authored teaching-material index names Vladimir Bulović as instructor. Lectures4–7 cover molecular levels, Franck-Condon factors, aggregate excitations and Frenkel excitons. These are reference notes, not this Cambridge paper's answers.

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]

A Frenkel exciton is a tightly bound electron–hole excitation localized on approximately one molecular or ionic unit. Its radius is comparable to the lattice spacing, its exciton binding energy can be large, and transport is described through transfer of the local excitation between units. Molecular solids such as crystalline anthracene provide a natural example: the optical excitation is largely associated with an individual molecule, so a broad parabolic-band hydrogen model is not the most useful starting point.

A Wannier-Mott exciton extends over many unit cells. It is described approximately by a conduction electron and a valence hole with effective masses and a dielectric-screened Coulomb attraction. Its binding is usually smaller, and its levels resemble a hydrogenic series. gallium arsenide is a suitable example because its direct-gap band-edge carriers have light effective masses and substantial dielectric dielectric screening, supporting spatially extended excitons. Localization length and dielectric screening, rather than whether a material happens to be called a semiconductor, distinguish the two limiting pictures. Real materials can lie between the limits, so neither family is a universal sharp classification.