Ab initio studies on acene tetramers: Herringbone structure

Abstract

The structures, energetics and transfer integrals of the acene tetramers up to pentacene are investigated with the ab initio molecular orbital method at the level of second-order Moller-Plesset perturbation theory (MP2). Calculated geometries for the herringbone-style structures found in the crystal structure were characterized as local minima, however the geometrical discrepancy between crystal and MP2 theoretical structure is reasonably small. The binding energy of pentacene tetramer was calculated up to 40 kcal/mol (MP2/6-31G(d)) and about 90 kcal/mol (MP2/aug-cc-pVDZ), and the latter seems to be too much overestimated. The tendency of the hole transfer integrals computed with ab initio MP2/3-21G(d) geometry is well agreement with those estimated with crystal structure with some discrepancy, and the gradual increment of the transfer integrals at the crystal geometry is attributed to mainly packing structure rather than the intrinsic property of acene such as a size of acene.