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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). 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
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:
Journal Article: 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:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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. Thu . "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). 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.},
doi = {10.1063/1.5038557},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 3,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

Quantum Embedding Theories
journal, November 2016


Nonadditive kinetic potentials from inverted Kohn-Sham problem
journal, June 2017

  • Banafsheh, Mojdeh; Adam Wesolowski, Tomasz
  • International Journal of Quantum Chemistry, Vol. 118, Issue 1
  • DOI: 10.1002/qua.25410

Ab initio density functional theory: OEP-MBPT(2). A new orbital-dependent correlation functional
journal, March 2002

  • Grabowski, Ireneusz; Hirata, So; Ivanov, Stanislav
  • The Journal of Chemical Physics, Vol. 116, Issue 11
  • DOI: 10.1063/1.1445117

Ab initio DFT: Getting the right answer for the right reason
journal, October 2006

  • Bartlett, Rodney J.; Schweigert, Igor V.; Lotrich, Victor F.
  • Journal of Molecular Structure: THEOCHEM, Vol. 771, Issue 1-3
  • DOI: 10.1016/j.theochem.2006.02.004

Embedded Correlated Wavefunction Schemes: Theory and Applications
journal, May 2014

  • Libisch, Florian; Huang, Chen; Carter, Emily A.
  • Accounts of Chemical Research, Vol. 47, Issue 9
  • DOI: 10.1021/ar500086h

Embedding a multideterminantal wave function in an orbital-free environment
journal, January 2008


Modelling charge transfer reactions with the frozen density embedding formalism
journal, December 2011

  • Pavanello, Michele; Neugebauer, Johannes
  • The Journal of Chemical Physics, Vol. 135, Issue 23
  • DOI: 10.1063/1.3666005

Charge-transfer in Symmetry-Adapted Perturbation Theory
journal, April 2009


Ab initio DFT and its role in electronic structure theory
journal, November 2010


Using the Constrained DFT Approach in Generating Diabatic Surfaces and Off Diagonal Empirical Valence Bond Terms for Modeling Reactions in Condensed Phases
journal, October 2006

  • Hong, Gongyi; Rosta, Edina; Warshel, Arieh
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp0625199

Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis
journal, January 2003

  • Fonseca Guerra, C�lia; Handgraaf, Jan-Willem; Baerends, Evert Jan
  • Journal of Computational Chemistry, Vol. 25, Issue 2
  • DOI: 10.1002/jcc.10351

eQE: An open-source density functional embedding theory code for the condensed phase: GENOVA et al.
journal, May 2017

  • Genova, Alessandro; Ceresoli, Davide; Krishtal, Alisa
  • International Journal of Quantum Chemistry, Vol. 117, Issue 16
  • DOI: 10.1002/qua.25401

A Simple, Exact Density-Functional-Theory Embedding Scheme
journal, July 2012

  • Manby, Frederick R.; Stella, Martina; Goodpaster, Jason D.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 8
  • DOI: 10.1021/ct300544e

Density Functional Partition Theory with Fractional Occupations
journal, March 2009

  • Elliott, Peter; Cohen, Morrel H.; Wasserman, Adam
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 4
  • DOI: 10.1021/ct9000119

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings
journal, February 2013

  • Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas
  • The Journal of Chemical Physics, Vol. 138, Issue 5
  • DOI: 10.1063/1.4789418

Ab Initio Frozen Density Functional Calculations of Proton Transfer Reactions in Solution
journal, January 1996

  • Wesolowski, Tomasz; Muller, Richard P.; Warshel, Arieh
  • The Journal of Physical Chemistry, Vol. 100, Issue 38
  • DOI: 10.1021/jp961068x

Partition density functional theory and its extension to the spin-polarized case
journal, October 2012


NBO 6.0 : Natural bond orbital analysis program
journal, March 2013

  • Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank
  • Journal of Computational Chemistry, Vol. 34, Issue 16
  • DOI: 10.1002/jcc.23266

Symmetry-adapted perturbation theory utilizing density functional description of monomers for high-spin open-shell complexes
journal, August 2008

  • Żuchowski, Piotr S.; Podeszwa, Rafał; Moszyński, Robert
  • The Journal of Chemical Physics, Vol. 129, Issue 8
  • DOI: 10.1063/1.2968556

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Charge Transfer from Regularized Symmetry-Adapted Perturbation Theory
journal, November 2013

  • Misquitta, Alston J.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 12
  • DOI: 10.1021/ct400704a

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

Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes
journal, November 1994

  • Jeziorski, Bogumil; Moszynski, Robert; Szalewicz, Krzysztof
  • Chemical Reviews, Vol. 94, Issue 7
  • DOI: 10.1021/cr00031a008

Constrained Density Functional Theory
journal, November 2011

  • Kaduk, Benjamin; Kowalczyk, Tim; Van Voorhis, Troy
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200148b

Ground-State Charge Transfer: Lithium–Benzene and the Role of Hartree–Fock Exchange
journal, October 2016

  • Borca, Carlos H.; Slipchenko, Lyudmila V.; Wasserman, Adam
  • The Journal of Physical Chemistry A, Vol. 120, Issue 41
  • DOI: 10.1021/acs.jpca.6b09014

Insights into Current Limitations of Density Functional Theory
journal, August 2008


Frozen-Density Embedding Strategy for Multilevel Simulations of Electronic Structure
journal, April 2015

  • Wesolowski, Tomasz A.; Shedge, Sapana; Zhou, Xiuwen
  • Chemical Reviews, Vol. 115, Issue 12
  • DOI: 10.1021/cr500502v

The exchange-correlation potential in ab initio density functional theory
journal, January 2005

  • Bartlett, Rodney J.; Grabowski, Ireneusz; Hirata, So
  • The Journal of Chemical Physics, Vol. 122, Issue 3
  • DOI: 10.1063/1.1809605

Potential-functional embedding theory for molecules and materials
journal, November 2011

  • Huang, Chen; Carter, Emily A.
  • The Journal of Chemical Physics, Vol. 135, Issue 19
  • DOI: 10.1063/1.3659293