Distributed multipole analysis

Abstract: Introduction 1. Molecules in Electrostatic Fields 2. Electrostatic Interactions between Molecules 3. Perturbation Theory of Intermolecular Forces at Long Range 4. Ab Initio Methods 5. Perturbation Theory of Intermolecular Forces at Short Range 6. Distributed Multipole Expansions 7. Distributed Polarizabilities 8. Many-body Effects and Intermolecular Forces in Solution 9. Interactions Involving Excited States 10. Practical Models for Intermolecular Potentials 11. Sources of Experimental Data Appendices: A Cartesian Tensors B Spherical Tensors C Introduction to Perturbation Theory D Conversion Factors E Cartesian-Spherical Conversion Tables F Interaction Functions

Abstract: A new classical empirical potential is proposed for water. The model uses a polarizable atomic multipole description of electrostatic interactions. Multipoles through the quadrupole are assigned to each atomic center based on a distributed multipole analysis (DMA) derived from large basis set molecular orbital calculations on the water monomer. Polarization is treated via self-consistent induced atomic dipoles. A modified version of Thole's interaction model is used to damp induction at short range. Repulsion−dispersion (vdW) effects are computed from a buffered 14−7 potential. In a departure from most current water potentials, we find that significant vdW parameters are necessary on hydrogen as well as oxygen. The new potential is fully flexible and has been tested versus a variety of experimental data and quantum calculations for small clusters, liquid water, and ice. Overall, excellent agreement with experimental and high level ab initio results is obtained for numerous properties, including cluster st...

Abstract: We extend the theory of dipole moments in crystalline insulators to higher multipole moments. In this paper, we expand in great detail the theory presented in Ref. 1, and extend it to cover associated topological pumping phenomena, and a novel class of 3D insulator with chiral hinge states. In quantum-mechanical crystalline insulators, higher multipole bulk moments manifest themselves by the presence of boundary-localized moments of lower dimension, in exact correspondence with the electromagnetic theory of classical continuous dielectrics. In the presence of certain symmetries, these moments are quantized, and their boundary signatures are fractionalized. These multipole moments then correspond to new SPT phases. The topological structure of these phases is described by "nested" Wilson loops, which reflect the bulk-boundary correspondence in a way that makes evident a hierarchical classification of the multipole moments. Just as a varying dipole generates charge pumping, a varying quadrupole generates dipole pumping, and a varying octupole generates quadrupole pumping. For non-trivial adiabatic cycles, the transport of these moments is quantized. An analysis of these interconnected phenomena leads to the conclusion that a new kind of Chern-type insulator exists, which has chiral, hinge-localized modes in 3D. We provide the minimal models for the quantized multipole moments, the non-trivial pumping processes and the hinge Chern insulator, and describe the topological invariants that protect them.