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Title: Extending density functional embedding theory for covalently bonded systems

Abstract

Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix–based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

Authors:
; ORCiD logo
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1411118
Alternate Identifier(s):
OSTI ID: 1527122
Grant/Contract Number:  
SC0002120
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 51; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING

Citation Formats

Yu, Kuang, and Carter, Emily A. Extending density functional embedding theory for covalently bonded systems. United States: N. p., 2017. Web. doi:10.1073/pnas.1712611114.
Yu, Kuang, & Carter, Emily A. Extending density functional embedding theory for covalently bonded systems. United States. doi:10.1073/pnas.1712611114.
Yu, Kuang, and Carter, Emily A. Mon . "Extending density functional embedding theory for covalently bonded systems". United States. doi:10.1073/pnas.1712611114.
@article{osti_1411118,
title = {Extending density functional embedding theory for covalently bonded systems},
author = {Yu, Kuang and Carter, Emily A.},
abstractNote = {Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix–based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.},
doi = {10.1073/pnas.1712611114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 51,
volume = 114,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1712611114

Citation Metrics:
Cited by: 3 works
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Figures / Tables:

Fig. 1 Fig. 1: Structures of cis– and trans–2-methyl-1,3,5-hexatriene, shown alongside retinal for comparison. The 2-methyl-1,3,5-hexatriene is the model molecule representing the central part of retinal encompassed in the dashed boxes. The ethenyl group within the blue boxes is treated as the environment in the ONIOM and DMFET calculations.

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Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Quantum Embedding Theories
journal, November 2016


Localized Atomic and Molecular Orbitals
journal, July 1963


Quantum mechanical embedding theory based on a unique embedding potential
journal, April 2011

  • Huang, Chen; Pavone, Michele; Carter, Emily A.
  • The Journal of Chemical Physics, Vol. 134, Issue 15
  • DOI: 10.1063/1.3577516

Density Matrix Embedding: A Strong-Coupling Quantum Embedding Theory
journal, February 2013

  • Knizia, Gerald; Chan, Garnet Kin-Lic
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 3
  • DOI: 10.1021/ct301044e

Advances in Correlated Electronic Structure Methods for Solids, Surfaces, and Nanostructures
journal, May 2008


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


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

Self-consistently determined properties of solids without band-structure calculations
journal, October 1991


A Limited Memory Algorithm for Bound Constrained Optimization
journal, September 1995

  • Byrd, Richard H.; Lu, Peihuang; Nocedal, Jorge
  • SIAM Journal on Scientific Computing, Vol. 16, Issue 5
  • DOI: 10.1137/0916069

The Description of Chemical Bonding From AB Initio Calculations
journal, October 1978


Remark on “algorithm 778: L-BFGS-B: Fortran subroutines for large-scale bound constrained optimization”
journal, November 2011

  • Morales, José Luis; Nocedal, Jorge
  • ACM Transactions on Mathematical Software, Vol. 38, Issue 1
  • DOI: 10.1145/2049662.2049669

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Exchange kinetic energy, contragradience, and chemical binding
journal, February 1970


Origin of the Energy Barrier to Chemical Reactions of O 2 on Al(111): Evidence for Charge Transfer, Not Spin Selection
journal, November 2012


Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H 2 on Au
journal, December 2012

  • Mukherjee, Shaunak; Libisch, Florian; Large, Nicolas
  • Nano Letters, Vol. 13, Issue 1
  • DOI: 10.1021/nl303940z

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Dissociative Adsorption of O 2 on Al(111): The Role of Orientational Degrees of Freedom
journal, April 2015

  • Cheng, Jin; Libisch, Florian; Carter, Emily A.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 9
  • DOI: 10.1021/acs.jpclett.5b00597

Inhomogeneous Electron Gas
journal, November 1964


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

Partition density-functional theory
journal, August 2010


Algorithm 778: L-BFGS-B: Fortran subroutines for large-scale bound-constrained optimization
journal, December 1997

  • Zhu, Ciyou; Byrd, Richard H.; Lu, Peihuang
  • ACM Transactions on Mathematical Software, Vol. 23, Issue 4
  • DOI: 10.1145/279232.279236

Subsystem density-functional theory: Subsystem density-functional theory
journal, July 2014

  • Jacob, Christoph R.; Neugebauer, Johannes
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 4
  • DOI: 10.1002/wcms.1175

Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems
journal, December 2016

  • Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele
  • The Journal of Chemical Physics, Vol. 145, Issue 24
  • DOI: 10.1063/1.4972012

Frozen density functional approach for ab initio calculations of solvated molecules
journal, July 1993

  • Wesolowski, Tomasz Adam; Warshel, Arieh
  • The Journal of Physical Chemistry, Vol. 97, Issue 30
  • DOI: 10.1021/j100132a040

QM/MM Methods for Biomolecular Systems
journal, January 2009

  • Senn, Hans Martin; Thiel, Walter
  • Angewandte Chemie International Edition, Vol. 48, Issue 7
  • DOI: 10.1002/anie.200802019

A direct optimization method for calculating density functionals and exchange–correlation potentials from electron densities
journal, January 2003

  • Wu, Qin; Yang, Weitao
  • The Journal of Chemical Physics, Vol. 118, Issue 6
  • DOI: 10.1063/1.1535422

Hohenberg-Kohn theorem for nonlocal external potentials
journal, September 1975


Bootstrap embedding: An internally consistent fragment-based method
journal, August 2016

  • Welborn, Matthew; Tsuchimochi, Takashi; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 145, Issue 7
  • DOI: 10.1063/1.4960986

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

Excited-State N 2 Dissociation Pathway on Fe-Functionalized Au
journal, March 2017

  • Martirez, John Mark P.; Carter, Emily A.
  • Journal of the American Chemical Society, Vol. 139, Issue 12
  • DOI: 10.1021/jacs.6b12301

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Density matrix embedding from broken symmetry lattice mean fields
journal, January 2014


Implementation of density functional embedding theory within the projector-augmented-wave method and applications to semiconductor defect states
journal, September 2015

  • Yu, Kuang; Libisch, Florian; Carter, Emily A.
  • The Journal of Chemical Physics, Vol. 143, Issue 10
  • DOI: 10.1063/1.4922260

The merits of the frozen-density embedding scheme to model solvatochromic shifts
journal, March 2005

  • Neugebauer, Johannes; Louwerse, Manuel J.; Baerends, Evert Jan
  • The Journal of Chemical Physics, Vol. 122, Issue 9
  • DOI: 10.1063/1.1858411

Quantum mechanical modeling of electronic excitations in metal oxides: Magnesia as a prototype
journal, January 2012


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Projection of plane-wave calculations into atomic orbitals
journal, September 1995


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