TY - JOUR

T1 - Force related atomic multipoles in planar molecules. Derivation of atomic quadrupole and octupole moments

AU - Dinur, Uri

PY - 1991/1/1

Y1 - 1991/1/1

N2 - Atomic multipoles as defined by current methods generally do not account for forces in molecules that arise from external electrostatic fields. It is pointed out that such forces and the electrostatic potential that the molecule itself generates are both determined by the molecular multipolar tensors. The latter constitute therefore the fundamental molecular constants that determine the molecular electrostatics apart from polarization. In general the multipolar tensors include contributions from the atomic multipoles and their fluxes. In planar molecules, however, the perpendicular charge flux is zero by symmetry. This gives rise to a (previously introduced) formalism that extracts analytical, force‐related, atomic multipoles from the molecular multipolar tensors. This formalism is extended in this work to include force‐related (FR) atomic quadrupoles and octupoles in planar molecules. The properties of the FR atomic multipoles, including their perpendicular fluxes, are discussed and some formal theoretical and computational advantages that characterize them are indicated. As an example, the electrostatics of OCS, including the molecular electrostatic potential and the forces on the nuclei due to an external point charge, is discussed.

AB - Atomic multipoles as defined by current methods generally do not account for forces in molecules that arise from external electrostatic fields. It is pointed out that such forces and the electrostatic potential that the molecule itself generates are both determined by the molecular multipolar tensors. The latter constitute therefore the fundamental molecular constants that determine the molecular electrostatics apart from polarization. In general the multipolar tensors include contributions from the atomic multipoles and their fluxes. In planar molecules, however, the perpendicular charge flux is zero by symmetry. This gives rise to a (previously introduced) formalism that extracts analytical, force‐related, atomic multipoles from the molecular multipolar tensors. This formalism is extended in this work to include force‐related (FR) atomic quadrupoles and octupoles in planar molecules. The properties of the FR atomic multipoles, including their perpendicular fluxes, are discussed and some formal theoretical and computational advantages that characterize them are indicated. As an example, the electrostatics of OCS, including the molecular electrostatic potential and the forces on the nuclei due to an external point charge, is discussed.

UR - http://www.scopus.com/inward/record.url?scp=84962354123&partnerID=8YFLogxK

U2 - 10.1002/jcc.540120110

DO - 10.1002/jcc.540120110

M3 - Article

AN - SCOPUS:84962354123

VL - 12

SP - 91

EP - 105

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 1

ER -