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Title: Beyond Born–Mayer: Improved Models for Short-Range Repulsion in ab Initio Force Fields

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3];  [1]
  1. Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States
  2. Department of Physics and Astronomy, Queen Mary University of London, London E1 4NS, United Kingdom
  3. Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom
+ Show Author Affiliations

Short-range repulsion within intermolecular force fields is conventionally described by either Lennard-Jones (A/r12) or Born–Mayer (A exp(-Br)) forms. Despite their widespread use, these simple functional forms are often unable to describe the interaction energy accurately over a broad range of intermolecular distances, thus creating challenges in the development of ab initio force fields and potentially leading to decreased accuracy and transferability. Herein, we derive a novel short-range functional form based on a simple Slater-like model of overlapping atomic densities and an iterated stockholder atom (ISA) partitioning of the molecular electron density. We demonstrate that this Slater–ISA methodology yields a more accurate, transferable, and robust description of the short-range interactions at minimal additional computational cost compared to standard Lennard-Jones or Born–Mayer approaches. Finally, we show how this methodology can be adapted to yield the standard Born–Mayer functional form while still retaining many of the advantages of the Slater-ISA approach.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014059
OSTI ID:
1299438
Alternate ID(s):
OSTI ID: 1259280; OSTI ID: 1433883
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Vol. 12 Journal Issue: 8; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 63 works
Citation information provided by
Web of Science

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