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Title: Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study

Abstract

We present a quantum Monte Carlo study of the hydrogen-benzene system where binding is very weak. We demonstrate that the binding is well described at both variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) levels by a Jastrow correlated single determinant geminal wave function with an optimized compact basis set that includes diffuse orbitals. Agreement between VMC and fixed-node DMC binding energies is found to be within 0.18mhartree, suggesting that the calculations are well converged with respect to the basis. Essentially the same binding is also found in independent DMC calculations using a different trial wave function of a more conventional Slater–Jastrow form, supporting our conclusion that the binding energy is accurate and includes all effects of correlation. Here, we compare with previous calculations, and we discuss the physical mechanisms of the interaction, the role of diffuse basis functions, and the charge redistribution in the bond.

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
  2. National Center for Supercomputing Applications, Urbana, IL (United States); Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
  3. International School for Advanced Studies, Trieste (Italy); DEMOCRITOS, National Simulation Center, Trieste (Italy)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC/ORNL, Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1564652
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 129; Journal Issue: 16; 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

Beaudet, Todd D., Casula, Michele, Kim, Jeongnim, Sorella, Sandro, and Martin, Richard M.. Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study. United States: N. p., 2008. Web. https://doi.org/10.1063/1.2987716.
Beaudet, Todd D., Casula, Michele, Kim, Jeongnim, Sorella, Sandro, & Martin, Richard M.. Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study. United States. https://doi.org/10.1063/1.2987716
Beaudet, Todd D., Casula, Michele, Kim, Jeongnim, Sorella, Sandro, and Martin, Richard M.. Tue . "Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study". United States. https://doi.org/10.1063/1.2987716. https://www.osti.gov/servlets/purl/1564652.
@article{osti_1564652,
title = {Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study},
author = {Beaudet, Todd D. and Casula, Michele and Kim, Jeongnim and Sorella, Sandro and Martin, Richard M.},
abstractNote = {We present a quantum Monte Carlo study of the hydrogen-benzene system where binding is very weak. We demonstrate that the binding is well described at both variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) levels by a Jastrow correlated single determinant geminal wave function with an optimized compact basis set that includes diffuse orbitals. Agreement between VMC and fixed-node DMC binding energies is found to be within 0.18mhartree, suggesting that the calculations are well converged with respect to the basis. Essentially the same binding is also found in independent DMC calculations using a different trial wave function of a more conventional Slater–Jastrow form, supporting our conclusion that the binding energy is accurate and includes all effects of correlation. Here, we compare with previous calculations, and we discuss the physical mechanisms of the interaction, the role of diffuse basis functions, and the charge redistribution in the bond.},
doi = {10.1063/1.2987716},
journal = {Journal of Chemical Physics},
number = 16,
volume = 129,
place = {United States},
year = {2008},
month = {10}
}

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Works referenced in this record:

On the Interaction of Dihydrogen with Aromatic Systems
journal, April 2004

  • Hübner, Olaf; Glöss, Andreas; Fichtner, Maximilian
  • The Journal of Physical Chemistry A, Vol. 108, Issue 15
  • DOI: 10.1021/jp031102p

Nanotechnological Aspects in Materials for Hydrogen Storage
journal, June 2005


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

Pair wave functions for strongly correlated fermions and their determinantal representation
journal, January 1988


Storage of hydrogen in single-walled carbon nanotubes
journal, March 1997

  • Dillon, A. C.; Jones, K. M.; Bekkedahl, T. A.
  • Nature, Vol. 386, Issue 6623
  • DOI: 10.1038/386377a0

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Microscopic Theory of Superconductivity
journal, April 1957


Hydrogen Storage in Novel Organometallic Buckyballs
journal, April 2005


Predicting the Heats of Formation of Model Hydrocarbons up to Benzene
journal, April 2000

  • Feller, David; Dixon, David A.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 13
  • DOI: 10.1021/jp994340m

Improved Theoretical Ground‐State Energy of the Hydrogen Molecule
journal, July 1968

  • Kolos, W.; Wolniewicz, L.
  • The Journal of Chemical Physics, Vol. 49, Issue 1
  • DOI: 10.1063/1.1669836

Quantum Monte Carlo simulations of solids
journal, January 2001


Transition metal oxides using quantum Monte Carlo
journal, July 2007


First-principles study of the rotational transitions of H[sub 2] physisorbed over benzene
journal, January 2004

  • Hamel, Sébastien; Côté, Michel
  • The Journal of Chemical Physics, Vol. 121, Issue 24
  • DOI: 10.1063/1.1813435

Backflow correlations for the electron gas and metallic hydrogen
journal, October 2003


Energetics and dipole moment of transition metal monoxides by quantum Monte Carlo
journal, January 2007

  • Wagner, Lucas K.; Mitas, Lubos
  • The Journal of Chemical Physics, Vol. 126, Issue 3
  • DOI: 10.1063/1.2428294

Diffusion Monte Carlo Method with Lattice Regularization
journal, September 2005


Energy-consistent pseudopotentials for quantum Monte Carlo calculations
journal, June 2007

  • Burkatzki, M.; Filippi, C.; Dolg, M.
  • The Journal of Chemical Physics, Vol. 126, Issue 23
  • DOI: 10.1063/1.2741534

Correlated geminal wave function for molecules: An efficient resonating valence bond approach
journal, October 2004

  • Casula, Michele; Attaccalite, Claudio; Sorella, Sandro
  • The Journal of Chemical Physics, Vol. 121, Issue 15
  • DOI: 10.1063/1.1794632

Generalized Lanczos algorithm for variational quantum Monte Carlo
journal, June 2001


Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007


Van der Waals Density Functional for General Geometries
journal, June 2004


Wave function optimization in the variational Monte Carlo method
journal, June 2005


Energy and Variance Optimization of Many-Body Wave Functions
journal, April 2005


Proof for an upper bound in fixed-node Monte Carlo for lattice fermions
journal, May 1995

  • ten Haaf, D. F. B.; van Bemmel, H. J. M.; van Leeuwen, J. M. J.
  • Physical Review B, Vol. 51, Issue 19
  • DOI: 10.1103/PhysRevB.51.13039

Geminal wave functions with Jastrow correlation: A first application to atoms
journal, October 2003

  • Casula, Michele; Sorella, Sandro
  • The Journal of Chemical Physics, Vol. 119, Issue 13
  • DOI: 10.1063/1.1604379

Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003

  • Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed
  • Science, Vol. 300, Issue 5622, p. 1127-1129
  • DOI: 10.1126/science.1083440

Electronic Structure
book, January 2004


Selective adsorption of 1H2 and 2H2 on the (0001) graphite surface
journal, March 1980


Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients
journal, October 1992


Computational studies of molecular hydrogen binding affinities: The role of dispersion forces, electrostatics, and orbital interactions
journal, January 2006

  • Lochan, Rohini C.; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 12
  • DOI: 10.1039/b515409j

Alleviation of the Fermion-Sign Problem by Optimization of Many-Body Wave Functions
journal, March 2007


Weak binding between two aromatic rings: Feeling the van der Waals attraction by quantum Monte Carlo methods
journal, July 2007

  • Sorella, Sandro; Casula, Michele; Rocca, Dario
  • The Journal of Chemical Physics, Vol. 127, Issue 1
  • DOI: 10.1063/1.2746035

Weak intermolecular interactions calculated with diffusion Monte Carlo
journal, November 2005

  • Diedrich, Christian; Lüchow, Arne; Grimme, Stefan
  • The Journal of Chemical Physics, Vol. 123, Issue 18
  • DOI: 10.1063/1.2110165

Molecular simulation of hydrogen adsorption in single-walled carbon nanotubes and idealized carbon slit pores
journal, January 1999

  • Wang, Qinyu; Johnson, J. Karl
  • The Journal of Chemical Physics, Vol. 110, Issue 1
  • DOI: 10.1063/1.478114

Laterally averaged interaction potentials for 1H2 and 2H2 on the (0001) graphite surface
journal, December 1982


Methods of conjugate gradients for solving linear systems
journal, December 1952

  • Hestenes, M. R.; Stiefel, E.
  • Journal of Research of the National Bureau of Standards, Vol. 49, Issue 6
  • DOI: 10.6028/jres.049.044

Beyond the locality approximation in the standard diffusion Monte Carlo method
journal, October 2006


Sharp Regularity Results for Coulombic Many-Electron Wave Functions
journal, January 2005

  • Fournais, S�ren; Hoffmann-Ostenhof, Maria; Hoffmann-Ostenhof, Thomas
  • Communications in Mathematical Physics, Vol. 255, Issue 1
  • DOI: 10.1007/s00220-004-1257-6

    Works referencing / citing this record:

    Quantum Monte Carlo for noncovalent interactions: an efficient protocol attaining benchmark accuracy
    journal, January 2014

    • Dubecký, Matúš; Derian, René; Jurečka, Petr
    • Phys. Chem. Chem. Phys., Vol. 16, Issue 38
    • DOI: 10.1039/c4cp02093f

    Complementary first and second derivative methods for ansatz optimization in variational Monte Carlo
    journal, January 2019

    • Otis, Leon; Neuscamman, Eric
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
    • DOI: 10.1039/c9cp02269d

    Resonating valence bond wave function with molecular orbitals: Application to first-row molecules
    journal, October 2009

    • Marchi, Mariapia; Azadi, Sam; Casula, Michele
    • The Journal of Chemical Physics, Vol. 131, Issue 15
    • DOI: 10.1063/1.3249966

    Properties of reactive oxygen species by quantum Monte Carlo
    journal, July 2014

    • Zen, Andrea; Trout, Bernhardt L.; Guidoni, Leonardo
    • The Journal of Chemical Physics, Vol. 141, Issue 1
    • DOI: 10.1063/1.4885144

    An accelerated linear method for optimizing non-linear wavefunctions in variational Monte Carlo
    journal, January 2020

    • Sabzevari, Iliya; Mahajan, Ankit; Sharma, Sandeep
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5125803

    Self-healing diffusion quantum Monte Carlo algorithms: Direct reduction of the fermion sign error in electronic structure calculations
    journal, May 2009