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Title: Quantum embedding for material chemistry based on domain separation and open subsystems

Abstract

Our perspective considers two theories we recently proposed to perform quantum embedding calculations for chemical systems: domain-separated density functional theory (DSDFT) and locally coupled open subsystems (LCOS). The development includes both the fundamentals of each theory as well as potential applications, some technical aspects, and related challenges. DS-DFT is suited to study intramolecular effects, where one can apply a high level of theory (based on DFT or wave function theory) to a region of interest inside a molecule or solid, and lower level theory elsewhere, with smooth switching between the regions. LCOS, in contrast, is a fragment-based embedding which offers computational advantages to study intermolecular behavior such as electron hopping, spin-environment interaction, and charge transfer excitations. Yet, both theories can exchange roles when appropriate. In addition, these theories allow for control of computational scaling of their algorithms. We investigate paths to determine the charge-transfer operator used in LCOS, and suggest an auxiliary energy minimization that can provide a practical estimate to this operator. We also briefly discuss how to implement density fitting techniques in domain separation, and how domain separation can be used for pure wavefunction-based embedding.

Authors:
ORCiD logo [1]; 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), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1598617
Alternate Identifier(s):
OSTI ID: 1600043
Grant/Contract Number:  
SC0004752; FG02‐03ER15457
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Quantum Chemistry
Additional Journal Information:
Journal Name: International Journal of Quantum Chemistry; Journal ID: ISSN 0020-7608
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; charge transfer; density functional theory; open subsystem; quantum embedding

Citation Formats

Mosquera, Martín A., Jones, Leighton O., Ratner, Mark A., and Schatz, George C. Quantum embedding for material chemistry based on domain separation and open subsystems. United States: N. p., 2020. Web. doi:10.1002/qua.26184.
Mosquera, Martín A., Jones, Leighton O., Ratner, Mark A., & Schatz, George C. Quantum embedding for material chemistry based on domain separation and open subsystems. United States. doi:10.1002/qua.26184.
Mosquera, Martín A., Jones, Leighton O., Ratner, Mark A., and Schatz, George C. Mon . "Quantum embedding for material chemistry based on domain separation and open subsystems". United States. doi:10.1002/qua.26184.
@article{osti_1598617,
title = {Quantum embedding for material chemistry based on domain separation and open subsystems},
author = {Mosquera, Martín A. and Jones, Leighton O. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {Our perspective considers two theories we recently proposed to perform quantum embedding calculations for chemical systems: domain-separated density functional theory (DSDFT) and locally coupled open subsystems (LCOS). The development includes both the fundamentals of each theory as well as potential applications, some technical aspects, and related challenges. DS-DFT is suited to study intramolecular effects, where one can apply a high level of theory (based on DFT or wave function theory) to a region of interest inside a molecule or solid, and lower level theory elsewhere, with smooth switching between the regions. LCOS, in contrast, is a fragment-based embedding which offers computational advantages to study intermolecular behavior such as electron hopping, spin-environment interaction, and charge transfer excitations. Yet, both theories can exchange roles when appropriate. In addition, these theories allow for control of computational scaling of their algorithms. We investigate paths to determine the charge-transfer operator used in LCOS, and suggest an auxiliary energy minimization that can provide a practical estimate to this operator. We also briefly discuss how to implement density fitting techniques in domain separation, and how domain separation can be used for pure wavefunction-based embedding.},
doi = {10.1002/qua.26184},
journal = {International Journal of Quantum Chemistry},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {2}
}

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