Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency

Mosquera, Martín A.; Ratner, Mark A.; Schatz, George C.

doi:10.1063/1.5038557

Title: Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency

Journal Article · Thu Jul 19 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5038557· OSTI ID:1540228

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Northwestern Univ., Evanston, IL (United States)

This manuscript introduces a methodology (within the Born-Oppenheimer picture) to compute electronic ground-state properties of molecules and solids/surfaces with fractionally occupied components. Given a user-defined division of the molecule into subsystems, our theory uses an auxiliary global Hamiltonian that is defined as the sum of subsystem Hamiltonians, plus the spatial integral of a second-quantized local operator that allows the electrons to be transferred between subsystems. This electron transfer operator depends on a local potential that can be determined using density functional approximations and/or other techniques such as machine learning. The present framework employs superpositions of tensor-product wave functions, which can satisfy size consistency and avoid spurious fractional charges at large bond distances. The electronic population of each subsystem is in general a positive real number and is obtained from wave-function amplitudes, which are calculated by means of ground-state matrix diagonalization (or matrix propagation in the time-dependent case). Furthermore, our method can provide pathways to explore charge-transfer effects in environments where dividing the molecule into subsystems is convenient and to develop computationally affordable electronic structure algorithms.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0004752

OSTI ID:: 1540228

Alternate ID(s):: OSTI ID: 1460915

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 3; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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