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Title: Partition-DFT on the water dimer

Abstract

As is well known, the ground-state symmetry group of the water dimer switches from its equilibrium Cs-character to C2h-character as the distance between the two oxygen atoms of the dimer decreases below RO–O~2.5 Å. For a range of RO–O between 1 and 5 Å, and for both symmetries, we apply Partition Density Functional Theory (PDFT) to find the unique monomer densities that sum to the correct dimer densities while minimizing the sum of the monomer energies. We calculate the work involved in deforming the isolated monomer densities and find that it is slightly larger for the Cs geometry for all RO–O. Finally, we discuss how the PDFT densities and the corresponding partition potentials support the orbital-interaction picture of hydrogen-bond formation.

Authors:
 [1];  [2];  [1];  [3]
  1. Univ. de Antioquia UdeA, Medellín (Colombia). Inst. de Química
  2. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  3. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry, and Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535298
Grant/Contract Number:  
SC0005291; FG02-10ER16191
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 7; 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

Gómez, Sara, Nafziger, Jonathan, Restrepo, Albeiro, and Wasserman, Adam. Partition-DFT on the water dimer. United States: N. p., 2017. Web. doi:10.1063/1.4976306.
Gómez, Sara, Nafziger, Jonathan, Restrepo, Albeiro, & Wasserman, Adam. Partition-DFT on the water dimer. United States. doi:10.1063/1.4976306.
Gómez, Sara, Nafziger, Jonathan, Restrepo, Albeiro, and Wasserman, Adam. Tue . "Partition-DFT on the water dimer". United States. doi:10.1063/1.4976306. https://www.osti.gov/servlets/purl/1535298.
@article{osti_1535298,
title = {Partition-DFT on the water dimer},
author = {Gómez, Sara and Nafziger, Jonathan and Restrepo, Albeiro and Wasserman, Adam},
abstractNote = {As is well known, the ground-state symmetry group of the water dimer switches from its equilibrium Cs-character to C2h-character as the distance between the two oxygen atoms of the dimer decreases below RO–O~2.5 Å. For a range of RO–O between 1 and 5 Å, and for both symmetries, we apply Partition Density Functional Theory (PDFT) to find the unique monomer densities that sum to the correct dimer densities while minimizing the sum of the monomer energies. We calculate the work involved in deforming the isolated monomer densities and find that it is slightly larger for the Cs geometry for all RO–O. Finally, we discuss how the PDFT densities and the corresponding partition potentials support the orbital-interaction picture of hydrogen-bond formation.},
doi = {10.1063/1.4976306},
journal = {Journal of Chemical Physics},
number = 7,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}

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Cited by: 11 works
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Works referenced in this record:

Studies of molecular association in H 2 O and D 2 O vapors by measurement of thermal conductivity
journal, September 1979

  • Curtiss, L. A.; Frurip, D. J.; Blander, M.
  • The Journal of Chemical Physics, Vol. 71, Issue 6
  • DOI: 10.1063/1.438628

Density-Based Partitioning Methods for Ground-State Molecular Calculations
journal, July 2014

  • Nafziger, Jonathan; Wasserman, Adam
  • The Journal of Physical Chemistry A, Vol. 118, Issue 36
  • DOI: 10.1021/jp504058s

Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds
journal, April 2010

  • Fux, Samuel; Jacob, Christoph R.; Neugebauer, Johannes
  • The Journal of Chemical Physics, Vol. 132, Issue 16
  • DOI: 10.1063/1.3376251

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

Development of transferable interaction models for water. I. Prominent features of the water dimer potential energy surface
journal, January 2002

  • Burnham, Christian J.; Xantheas, Sotiris S.
  • The Journal of Chemical Physics, Vol. 116, Issue 4
  • DOI: 10.1063/1.1423940

Structural Studies of the Water Hexamer
journal, July 2010

  • Hincapié, Gina; Acelas, Nancy; Castaño, Marcela
  • The Journal of Physical Chemistry A, Vol. 114, Issue 29
  • DOI: 10.1021/jp103683m

Structures, energies, and bonding in the water heptamer
journal, July 2013

  • Acelas, Nancy; Hincapié, Gina; Guerra, Doris
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4816371

Accurate Reference Data for the Nonadditive, Noninteracting Kinetic Energy in Covalent Bonds
journal, January 2017

  • Nafziger, Jonathan; Jiang, Kaili; Wasserman, Adam
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b01050

Structural studies of the water tetramer
journal, January 2008

  • Pérez, Jhon F.; Hadad, C. Z.; Restrepo, Albeiro
  • International Journal of Quantum Chemistry, Vol. 108, Issue 10
  • DOI: 10.1002/qua.21615

Molecular interactions in the microsolvation of dimethylphosphate
journal, August 2015


Water clusters: Untangling the mysteries of the liquid, one molecule at a time
journal, September 2001

  • Keutsch, F. N.; Saykally, R. J.
  • Proceedings of the National Academy of Sciences, Vol. 98, Issue 19
  • DOI: 10.1073/pnas.191266498

On the Foundations of Chemical Reactivity Theory
journal, March 2007

  • Cohen, Morrel H.; Wasserman, Adam
  • The Journal of Physical Chemistry A, Vol. 111, Issue 11
  • DOI: 10.1021/jp066449h

Fragment occupations in partition density functional theory
journal, January 2012

  • Tang, Rougang; Nafziger, Jonathan; Wasserman, Adam
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 21
  • DOI: 10.1039/c2cp23994a

Partially deuterated water dimers: Microwave spectra and structure
journal, May 1980

  • Odutola, J. A.; Dyke, T. R.
  • The Journal of Chemical Physics, Vol. 72, Issue 9
  • DOI: 10.1063/1.439795

Kohn-Sham equations with constrained electron density: an iterative evaluation of the ground-state electron density of interacting molecules
journal, January 1996


Analysis of weakly bound structures: hydrogen bond and the electron density in a water dimer
journal, December 2003


Transition structures for the interchange of hydrogen atoms within the water dimer
journal, January 1990

  • Smith, Brian J.; Swanton, David J.; Pople, John A.
  • The Journal of Chemical Physics, Vol. 92, Issue 2
  • DOI: 10.1063/1.458133

Partition density-functional theory
journal, August 2010


Very weak interactions: structures, energies and bonding in the tetramers and pentamers of hydrogen sulfide
journal, January 2014

  • Ibargüen, César; Guerra, Doris; Hadad, C. Z.
  • RSC Adv., Vol. 4, Issue 102
  • DOI: 10.1039/c4ra09430a

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

The Importance of Being Inconsistent
journal, May 2017


Partition Theory:  A Very Simple Illustration
journal, December 2007

  • Cohen, Morrel H.; Wasserman, Adam; Burke, Kieron
  • The Journal of Physical Chemistry A, Vol. 111, Issue 49
  • DOI: 10.1021/jp0743370

Intermolecular potential functions and the properties of water
journal, January 1982


Molecular binding energies from partition density functional theory
journal, December 2011

  • Nafziger, Jonathan; Wu, Qin; Wasserman, Adam
  • The Journal of Chemical Physics, Vol. 135, Issue 23
  • DOI: 10.1063/1.3667198

The structure of water dimer from molecular beam electric resonance spectroscopy
journal, January 1977

  • Dyke, Thomas R.; Mack, Kenneth M.; Muenter, J. S.
  • The Journal of Chemical Physics, Vol. 66, Issue 2
  • DOI: 10.1063/1.433969

Embedded density functional theory for covalently bonded and strongly interacting subsystems
journal, April 2011

  • Goodpaster, Jason D.; Barnes, Taylor A.; Miller, Thomas F.
  • The Journal of Chemical Physics, Vol. 134, Issue 16
  • DOI: 10.1063/1.3582913

Fragment-based treatment of delocalization and static correlation errors in density-functional theory
journal, December 2015

  • Nafziger, Jonathan; Wasserman, Adam
  • The Journal of Chemical Physics, Vol. 143, Issue 23
  • DOI: 10.1063/1.4937771

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


On Hardness and Electronegativity Equalization in Chemical Reactivity Theory
journal, April 2006


The Water Dipole Moment in Water Clusters
journal, February 1997


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

Microwave spectral tables II. Triatomic molecules
journal, October 1978

  • Lovas, Frank J.
  • Journal of Physical and Chemical Reference Data, Vol. 7, Issue 4
  • DOI: 10.1063/1.555588

Natural bond orbital analysis of near‐Hartree–Fock water dimer
journal, March 1983

  • Reed, Alan E.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 78, Issue 6
  • DOI: 10.1063/1.445134

The water dimer I: Experimental characterization
journal, July 2015


A systematic ab initio study of the water dimer in hierarchies of basis sets and correlation models
journal, October 1997

  • Halkier, Asger; Koch, Henrik; Jørgensen, Poul
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4
  • DOI: 10.1007/s002140050248

Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988

  • Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
  • Chemical Reviews, Vol. 88, Issue 6
  • DOI: 10.1021/cr00088a005

Structural studies of the water pentamer
journal, May 2011


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    Partition potential for hydrogen bonding in formic acid dimers
    journal, October 2018

    • Gómez, Sara; Oueis, Yan; Restrepo, Albeiro
    • International Journal of Quantum Chemistry, Vol. 119, Issue 4
    • DOI: 10.1002/qua.25814

    Fe 3+ chelating quinoline–hydrazone hybrids with proven cytotoxicity, leishmanicidal, and trypanocidal activities
    journal, January 2018

    • Coa, Juan Carlos; Cardona-Galeano, Wilson; Restrepo, Albeiro
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 31
    • DOI: 10.1039/c8cp04174a

    Antioxidant activity of curcuminoids
    journal, January 2019

    • Llano, Sandra; Gómez, Sara; Londoño, Julián
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 7
    • DOI: 10.1039/c8cp06708b

    Development of formalisms based on locally coupled open subsystems for calculations in molecular electronic structure and dynamics
    journal, December 2018