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Title: Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations

Abstract

We recently proposed Domain Separated Density Functional Theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. Here, this work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: i), the screened-density approximation (SDA), and, ii), linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1798256
Grant/Contract Number:  
SC0004752; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 124; Journal Issue: 28; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical reactions; Embedding; Energy; Chemical calculations; Approximation

Citation Formats

Mosquera, Martín A., Jones, Leighton O., Borca, Carlos H., Ratner, Mark A., and Schatz, George C. Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations. United States: N. p., 2020. Web. doi:10.1021/acs.jpca.0c03596.
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Mosquera, Martín A., Jones, Leighton O., Borca, Carlos H., Ratner, Mark A., & Schatz, George C. Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations. United States. https://doi.org/10.1021/acs.jpca.0c03596
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Mosquera, Martín A., Jones, Leighton O., Borca, Carlos H., Ratner, Mark A., and Schatz, George C. Tue . "Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations". United States. https://doi.org/10.1021/acs.jpca.0c03596. https://www.osti.gov/servlets/purl/1798256.
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@article{osti_1798256,
title = {Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations},
author = {Mosquera, Martín A. and Jones, Leighton O. and Borca, Carlos H. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {We recently proposed Domain Separated Density Functional Theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. Here, this work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: i), the screened-density approximation (SDA), and, ii), linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.},
doi = {10.1021/acs.jpca.0c03596},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 124,
place = {United States},
year = {Tue Jun 16 00:00:00 EDT 2020},
month = {Tue Jun 16 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpca.0c03596
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Works referenced in this record:

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

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

Quantum-chemical embedding methods for treating local electronic excitations in complex chemical systems
journal, January 2012

  • Severo Pereira Gomes, André; Jacob, Christoph R.
  • Annual Reports Section "C" (Physical Chemistry), Vol. 108
  • DOI: 10.1039/c2pc90007f

Detection and Electronic Structure of Naked Actinide Complexes: Rhombic-Ring (AnN) 2 Molecules Stabilized by Delocalized π-Bonding
journal, January 2016

  • Vlaisavljevich, Bess; Andrews, Lester; Wang, Xuefeng
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b10458

Domain Separation in Density Functional Theory
journal, May 2019

  • Mosquera, Martín A.; Jones, Leighton O.; Borca, Carlos H.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 22
  • DOI: 10.1021/acs.jpca.9b01173

Quantum embedding for material chemistry based on domain separation and open subsystems
journal, February 2020

  • Mosquera, Martín A.; Jones, Leighton O.; Ratner, Mark A.
  • International Journal of Quantum Chemistry, Vol. 120, Issue 21
  • DOI: 10.1002/qua.26184

Double-hybrid density functionals: Double-hybrid density functionals
journal, July 2014

  • Goerigk, Lars; Grimme, Stefan
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 6
  • DOI: 10.1002/wcms.1193

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

Hubbard model in infinite dimensions
journal, March 1992

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

Generalization of the Kohn-Sham equations with constrained electron density formalism and its time-dependent response theory formulation
journal, January 2003

  • Casida, Mark E.; Weso?owski, Tomasz A.
  • International Journal of Quantum Chemistry, Vol. 96, Issue 6
  • DOI: 10.1002/qua.10744

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

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

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 Matrix Embedding: A Simple Alternative to Dynamical Mean-Field Theory
journal, November 2012

Multi-configuration time-dependent density-functional theory based on range separation
journal, February 2013

  • Fromager, Emmanuel; Knecht, Stefan; Jensen, Hans Jørgen Aa.
  • The Journal of Chemical Physics, Vol. 138, Issue 8
  • DOI: 10.1063/1.4792199

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

Large-Scale Computations in Chemistry: A Bird’s Eye View of a Vibrant Field
journal, April 2015

  • Akimov, Alexey V.; Prezhdo, Oleg V.
  • Chemical Reviews, Vol. 115, Issue 12
  • DOI: 10.1021/cr500524c

Local density approximation in site-occupation embedding theory
journal, May 2016

Multiple impurities and combined local density approximations in site-occupation embedding theory
journal, November 2018

  • Senjean, Bruno; Nakatani, Naoki; Tsuchiizu, Masahisa
  • Theoretical Chemistry Accounts, Vol. 137, Issue 12
  • DOI: 10.1007/s00214-018-2368-z

Combining long-range configuration interaction with short-range density functionals
journal, August 1997

Generalized Kohn-Sham schemes and the band-gap problem
journal, February 1996

Embedding Methods for Quantum Chemistry: Applications from Materials to Life Sciences
journal, January 2020

  • Jones, Leighton O.; Mosquera, Martín A.; Schatz, George C.
  • Journal of the American Chemical Society, Vol. 142, Issue 7
  • DOI: 10.1021/jacs.9b10780

Sequential double excitations from linear-response time-dependent density functional theory
journal, May 2016

  • Mosquera, Martín A.; Chen, Lin X.; Ratner, Mark A.
  • The Journal of Chemical Physics, Vol. 144, Issue 20
  • DOI: 10.1063/1.4950876

Time-Dependent Density Functional Response Theory for Molecules
book, November 1995

The SIESTA method; developments and applicability
journal, January 2008

The SIESTA method for ab initio order- N materials simulation
journal, March 2002

  • Soler, José M.; Artacho, Emilio; Gale, Julian D.
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 11
  • DOI: 10.1088/0953-8984/14/11/302

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

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

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
  • DOI: 10.1007/BF00533485

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267

Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements
journal, January 1980

  • Binkley, J. Stephen; Pople, John A.; Hehre, Warren J.
  • Journal of the American Chemical Society, Vol. 102, Issue 3
  • DOI: 10.1021/ja00523a008

A doubles correction to electronic excited states from configuration interaction in the space of single substitutions
journal, March 1994

The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Software update: the ORCA program system, version 4.0: Software update
journal, July 2017

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1
  • DOI: 10.1002/wcms.1327

Prediction of transition state barriers and enthalpies of reaction by a new hybrid density-functional approximation
journal, December 2001

  • Kang, Jeung Ku; Musgrave, Charles B.
  • The Journal of Chemical Physics, Vol. 115, Issue 24
  • DOI: 10.1063/1.1415079

A detailed analysis of the Raman enhancement mechanisms associated with the interaction of a Raman scatterer with a resonant metal cluster: Results for Li n –H 2
journal, March 1984

  • Pandey, Prabhat K. K.; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 80, Issue 6
  • DOI: 10.1063/1.447045

Connection between Hybrid Functionals and Importance of the Local Density Approximation
journal, February 2016

  • Mosquera, Martín A.; Borca, Carlos H.; Ratner, Mark A.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 9
  • DOI: 10.1021/acs.jpca.5b10864

Note on Exchange Phenomena in the Thomas Atom
journal, July 1930

  • Dirac, P. A. M.
  • Mathematical Proceedings of the Cambridge Philosophical Society, Vol. 26, Issue 3
  • DOI: 10.1017/S0305004100016108

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

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

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

Control of Charge Carriers and Band Structure in 2D Monolayer Molybdenum Disulfide via Covalent Functionalization
journal, January 2020

  • Jones, Leighton O.; Mosquera, Martín A.; Ratner, Mark A.
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 4
  • DOI: 10.1021/acsami.9b19639
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