Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic contributions is extended from spherical to ellipsoidal atomic basins. Despite the more flexible parametrization, the derived atomic multipole moments do not systematically improve the reproduction of molecular multipole moments and electrostatic potentials relative to a decomposition into spherical atomic densities. The decomposition can be constrained to exactly reproduce molecular multipole moments, in the present work extended up to hexadecapole moments, and this slightly improves the ability to reproduce the electrostatic potential. A byproduct of the ellipsoidal decomposition is a set of atomic parameters that describe the anisotropic decay of the electron density with distance from the nucleus, and this may be useful in developing anisotropic atomic parameters for use in force fields as well as for defining anisotropic atomic densities for use in quantum crystallography.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jctc.5c00788 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Minimal Basis Iterative Stockholder Decomposition with Ellipsoidal Atoms.
J Chem Theory Comput
September 2025
Department of Chemistry, Aarhus University, DK-8000 Aarhus, Denmark.
The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic contributions is extended from spherical to ellipsoidal atomic basins. Despite the more flexible parametrization, the derived atomic multipole moments do not systematically improve the reproduction of molecular multipole moments and electrostatic potentials relative to a decomposition into spherical atomic densities. The decomposition can be constrained to exactly reproduce molecular multipole moments, in the present work extended up to hexadecapole moments, and this slightly improves the ability to reproduce the electrostatic potential.
View Article and Find Full Text PDFModeling water using multipole response tensors fitted to the monomer geometry.
J Chem Phys
September 2025
Department of Physics, Stockholm University, 10691 Stockholm, Sweden.
The water molecule's electronic Cartesian multipole moment and polarizability tensors have been fitted with Gaussian process regression to the internal coordinates and are used to evaluate accurate electrostatic, induction, and dispersion energy components between flexible molecules. The model yields a handful of damping and scaling parameters that were adjusted for the energy components to agree with 2-body symmetry-adapted perturbation theory decomposition and then fine-tuned in order for the total energy to agree with CCSD(T) for small clusters. We present a simple algorithm for rotating symmetric Cartesian tensors and employ a dispersion potential based on multipole polarizabilities.
View Article and Find Full Text PDFUnderstanding the role of short- and long-range intermolecular interactions in novel computational drug discovery.
Expert Opin Drug Discov
August 2025
Department of Chemistry, Wake Forest University, Winston-Salem, NC, USA.
Introduction: Understanding the interactions between functional groups, ligands, molecular fragments, as well as whole molecules, is critical in modern drug discovery. Key to this endeavor is the theoretical development of the fundamental inter-particle forces in play and their implementation in numerous software packages that allow the calculation of interaction energies at varying levels of theory ranging from the entirely classical at one extreme to the fully quantum mechanical at the other.
Areas Covered: In this review, the authors consider the concept of an intermolecular potential energy function and its separation into short- and long-range regions.
Phonon-Driven Multipolar Dynamics in a Spin-Orbit Coupled Mott Insulator.
Phys Rev Lett
June 2025
University of Toronto, Department of Physics, 60 Saint George Street, Toronto, Ontario M5S 1A7, Canada.
Motivated by advances in pump-probe experiments and light-driven phenomena, we theoretically study the impact of pumped and driven phonons in Mott insulators which host multipole moments, thus going beyond conventional dipolar magnetism. As a case study, we examine pseudospin-1/2 Mott insulators hosting quadrupolar and octupolar moments, and investigate the effect of resonantly exciting E_{g} phonon modes which couple linearly to the quadrupoles. We show that this leads to multipolar precession, with the backaction resulting in pseudochiral phonon dynamics in the octupolar ordered phase.
View Article and Find Full Text PDFInsights from the Absorption Coefficient for the Development of Polarizable (Multipole) Force Fields.
Molecules
July 2025
Department of Computational Biological Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 17, 1090 Vienna, Austria.
We present a detailed examination of the absorption coefficients in the THz region for different water models using different types of potentials: the non-polarizable SPC/E, the Drude-polarizable SWM4-NDP and OPC3-pol, IPOL-0.13 and the multipole AMOEBA14 water. The primary focus is on understanding the interplay between permanent and induced dipole moments and their influence on the THz spectrum.
View Article and Find Full Text PDF