M. Andrzejak et al., Quantum chemical results as input for solid state calculations: charge transfer states in molecular crystals, J MOL ST-TH, 527, 2000, pp. 91-102
The difference I - A between the ionization potential and electron affinity
of a molecule is one of the input parameters necessary for calculating the
energies of charge transfer states in molecular crystals. In the present p
aper, the performance of the DFT methodology with several alternative forms
of the exchange-correlation potential is tested in this context. Calculati
ons are carried out for polyacenes to select the best potentials and to set
up a scheme for correcting systematic errors of the approach, which is sub
sequently used to calculate the relevant quantity for sexithiophene and per
ylenetetracarboxylic dianhydride (PTCDA). Combined with independent calcula
tions of the electrostatic energy of charge pairs in these crystals, the re
sults are confronted with CT state energies observed in electro-absorption
spectroscopy. (C) 2000 Elsevier Science B.V. All rights reserved.