Exchange potentials for semi-classical electrons

Literature Information

Publication Date 2016-10-20
DOI 10.1039/C6CP06100A
Impact Factor 3.676
Authors

Judith Herzfeld, Solen Ekesan


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Abstract

Semi-classical electrons offer access to efficient and intuitive simulations of chemical reactions. As for any treatment of fermions, the greatest difficulty is in accounting for anti-symmetry effects. Semi-classical efforts to-date either reference Slater-determinants from ab initio treatments or adopt a heuristic approach inspired by density functional treatments. Here we revisit the problem with a combined approach. We conclude that semi-classical electrons need to reference a non-conventional wave function and find that (1) contrary to earlier suppositions, contributions from the electrostatic terms in the Hamiltonian are of similar magnitude to those from the kinetic terms and (2) the former point to a need to supplement pair potentials with 3-body potentials. The first result explains features of reported heuristic potentials, and the second provides a firm footing for extending the transferability of potentials across a wider range of elements and bonding scenarios.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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