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

Abstract

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). 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry and the Materials Research Center, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208, USA
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540228
Alternate Identifier(s):
OSTI ID: 1460915
Grant/Contract Number:  
SC0004752
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Mosquera, Martín A., Ratner, Mark A., and Schatz, George C. Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency. United States: N. p., 2018. Web. doi:10.1063/1.5038557.
Mosquera, Martín A., Ratner, Mark A., & Schatz, George C. Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency. United States. doi:10.1063/1.5038557.
Mosquera, Martín A., Ratner, Mark A., and Schatz, George C. Sat . "Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency". United States. doi:10.1063/1.5038557. https://www.osti.gov/servlets/purl/1540228.
@article{osti_1540228,
title = {Locally coupled open subsystems: A formalism for affordable electronic structure calculations featuring fractional charges and size consistency},
author = {Mosquera, Martín A. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {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). 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.},
doi = {10.1063/1.5038557},
journal = {Journal of Chemical Physics},
number = 3,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018