Chemical accuracy from quantum Monte Carlo for the benzene dimer
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Published version
Author(s)
Azadi, S
Cohen, RE
Type
Journal Article
Abstract
We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of −2.3(4) and −2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is −2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.
Date Issued
2015-09-08
Date Acceptance
2015-08-24
Citation
Journal of Chemical Physics, 2015, 143 (10)
ISSN
1089-7690
Publisher
American Institute of Physics
Journal / Book Title
Journal of Chemical Physics
Volume
143
Issue
10
Copyright Statement
© 2015 AIP Publishing LLC. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Journal of Chemical Physics and may be found at http://dx.doi.org/10.1063/1.4930137.
Subjects
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
104301