The main optical, dark and photoconductivity, photo‐emf, and photoemission characteristics are studied for thin‐layers of pentacene (Pc) crystals. It is shown that in the h = = 2.2 to 4.0 eV spectral region intrinsic photogeneration is dominant in Pc crystals, presumably proceeding via an autoionization mechanisms with a threshold value Ec = = (2.20 ± 0.05) eV. Whereas in the hvv = 1.4 to 2.2 eV spectral region an exciton photogeneration mechanism, namely, generation of excess charge carriers through triplet exciton‐trapped hole interaction, seems most probably. The energy level spectra of neutral and ionized states of the Pc crystal are determined. The Pc crystal ionization energy Ic equals to (5.07 ± 0.05) eV; the forbidden energy gap ΔE0 = (2.20 ± 0.05) eV; the intrinsic dark conductivity activation energy E a0 = ΔE0/2 = (1.15 ± 0.15) eV. The electron affinity Ac of the Pc crystal, determined by three independent methods equals to (2.87 ± 0.10) eV, (2.70 ± 0.15) eV, or (2.73 ± 0.2) eV, respectively. The characteristic energies of the quasi‐continuous trap distribution for vacuum evaporated thin Pc crystals layers are kTc = 0.12 eV in an exponential approximation and ± = 0.28 eV in a Gaussian one as determined from SCLC measurements.

An extended phenomenological model of photogeneration mechanisms in organic molecular crystals is proposed which describes intermediate and final stages of multi‐step photogeneration processes in terms of a modified Onsager approach. It is shown that the intermediate geminate charge pair (CP) states can be populated through two independent competitive pathways: viz. via autoionization and subsequent hot electron thermalization in terms of a ballistic model and via optical charge transfer (CT) transitions. The thermalization processes and their dependence on photon energy, temperature, and electric field are studied in some detail. It is demonstrated that the threshold spectral dependence of intrinsic photoconductivity quantum efficiency β(hv) in anthracene‐type crystals is mainly determined by the spectral dependence of dissociation efficiency Ω(hv) of the intermediate CP‐states and can be approximated by Onsager's formula.