Band structure of the four pentacene polymorphs and effect on the hole mobility at low temperature.

The band structure of the four known polymorphs of pentacene is computed from first principles using the accurate molecular orbitals of the isolated molecule as the basis for the calculation of the crystalline orbitals. The computed bands are remarkably different for each polymorph, but their diversity can be easily rationalized using a simple analytical model that employs only three parameters. The effect of the electronic structure on the hole mobility was evaluated using a simple model based on the constant relaxation time approximation. It is found that the mobility tensor is highly anisotropic for three of the four considered polymorphs. The practical implication of this prediction on the technology of thin-film organic transistors is discussed.