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  • Revisiting the N ( N  + 1)/2‐site s ‐type Gaussian charge model for permutationally invariant polynomial fitting of global molecular tensor surfaces
Title: Revisiting the N ( N  + 1)/2‐site s ‐type Gaussian charge model for permutationally invariant polynomial fitting of global molecular tensor surfaces
Abstract The exact expressions for the dipole, quadrupole, and octupoles of a collection ofNpoint charges involve summations of corresponding tensors over theNsites weighted by their charge magnitudes. When the point charges are atoms (in a molecule) theN‐site formula is an approximation, and one must integrate over the electron density to recover the exact multipoles. In the present work we revisit theN(N + 1)/2‐site point charge density model of Hall (Chem. Phys. Lett.6, 501, 1973) for the purpose of fitting ab initio derived multipole moment hypersurfaces using permutationally invariant polynomials (PIP). We examine new approaches in PIP‐fitting procedures for the dipole, quadrupole, octupole moments, and polarizability tensor surfaces (DMS, QMS, OMS and PTS, respectively) for a non‐polar CCl4and a polar CHCl3and show that compared to the primitiveN‐site model theN(N + 1)/2‐site model appreciably improves the relative RMSE of the DMS and does much more substantially so, by an order of magnitude, for the corresponding ones of QMS and OMS. Training datasets are obtained by sampling potential energies up to 18 000 cm−1above the global minima, generated by molecular dynamics simulations at the DFT B3LYP/aug‐cc‐pVDZ level of theory.  more » « less
Award ID(s):
1855583
PAR ID:
10473172
Author(s) / Creator(s):
; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
International Journal of Quantum Chemistry
Volume:
123
Issue:
11
ISSN:
0020-7608
Subject(s) / Keyword(s):
permutationally invariant polynomials, polarizability, fitting global surfaces
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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