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Title: Energy benchmarks for methane-water systems from quantum Monte Carlo and second-order Møller-Plesset calculations

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.4926444 · OSTI ID:1565342
 [1]; ORCiD logo [2];  [3]
  1. Univ. College London (UCL), Bloomsbury (United Kingdom). London Centre for Nanotechnology, Dept. of Physics and Astronomy, and Thomas Young Centre
  2. Univ. College London (UCL), Bloomsbury (United Kingdom). London Centre for Nanotechnology, Dept. of Physics and Astronomy, Thomas Young Centre, and Dept. of Earth Sciences
  3. Bristol Univ. (United Kingdom). School of Chemistry
+ Show Author Affiliations

The quantum Monte Carlo (QMC) method is used to generate accurate energy benchmarks for methane-water clusters containing a single methane monomer and up to 20 water monomers. The benchmarks for each type of cluster are computed for a set of geometries drawn from molecular dynamics simulations. The accuracy of QMC is anticipated to be comparable with that of coupled-cluster calculations, and this is confirmed by comparisons for the CH4-H2O dimer. The benchmarks are used to assess the accuracy of the second-order Møller-Plesset (MP2) approximation close to the complete basis-set limit. A recently created embedded many-body technique is shown to give an efficient procedure for computing basis-set converged MP2 energies for the large clusters. It is found that MP2 values for the methane binding energies and the cohesive energies of the water clusters without methane are in close agreement with the QMC benchmarks, but the agreement is aided by partial cancelation between 2-body and beyond-2-body errors of MP2. The embedding approach allows MP2 to be applied without loss of accuracy to the methane hydrate crystal, and it is shown that the resulting methane binding energy and the cohesive energy of the water lattice agree almost exactly with recently reported QMC values

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1565342
Alternate ID(s):
OSTI ID: 1228782
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 10; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

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Properties of the water to boron nitride interaction: from zero to two dimensions with benchmark accuracy text January 2017
Toward Accurate Adsorption Energetics on Clay Surfaces journal November 2016
A comparison between quantum chemistry and quantum Monte Carlo techniques for the adsorption of water on the (001) LiH surface journal May 2017
Pressure and stress tensor of complex anharmonic crystals within the stochastic self-consistent harmonic approximation text January 2018
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