Atomic multipolar contributions to electronic polarization in
organic molecular crystals
J.M. Sin, E.V. Tsiper, and Z.G. Soos
Department of Chemistry, Princeton University, Princeton, NJ 08544
The self-consistent computation of electronic polarization in organic
molecular crystals is extended to include, in first order, corrections
in the continuous gas-phase charge distribution
ρG(r). The potential
ΔΦa(ra) at molecule a in the
crystal is due to the difference between ρG(r)
and a point-charge approximation.
ΔΦa(ra), which represents atomic
multipolar contributions, is evaluated for crystals of anthracene and
perylenetetracarboxylic dianhydride (PTCDA). The corrections to the
polarization energies of molecular cations are
P+(1)=-0.25 and -0.14 eV for anthracene and
PTCDA, respectively, while P-(1)=0.25 and 0.18
eV for the anions. The leading term of atomic multipoles is the
ΔΦa(ra)-charge interaction that
corresponds to the charge-quadrupole term in the submolecular
approach. There are also new contributions in
ΔΦa(ra)-redistributed-charge and
coupling of induced dipoles to gradients of
ΔΦa(ra). First-order correction
to electronic polarization is a general approach that combines the
advantages of discrete charges for self-consistent treatment of
crystals with accurate electrostatic potentials based on the best
available molecular charge distribution.
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