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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2987716· OSTI ID:1564652
 [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)
+ Show Author Affiliations

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC/ORNL, Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1564652
Journal Information:
Journal of Chemical Physics, Vol. 129, Issue 16; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science

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Cited By (10)

Quantum Monte Carlo for noncovalent interactions: an efficient protocol attaining benchmark accuracy journal January 2014
Complementary first and second derivative methods for ansatz optimization in variational Monte Carlo journal January 2019
Resonating valence bond wave function with molecular orbitals: Application to first-row molecules journal October 2009
Properties of reactive oxygen species by quantum Monte Carlo journal July 2014
An accelerated linear method for optimizing non-linear wavefunctions in variational Monte Carlo journal January 2020
Self-healing diffusion quantum Monte Carlo algorithms: Direct reduction of the fermion sign error in electronic structure calculations journal May 2009
Self-healing diffusion quantum Monte Carlo algorithms: methods for direct reduction of the fermion sign error in electronic structure calculations text January 2008
Quantum Monte Carlo for Noncovalent Interactions: An Efficient Protocol Attaining Benchmark Accuracy text January 2014
Essentially exact ground-state calculations by superpositions of nonorthogonal Slater determinants journal May 2013
An accelerated linear method for optimizing non-linear wavefunctions in variational Monte Carlo text January 2019

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