title: Chemical accuracy from quantum Monte Carlo for the benzene dimer.
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.
authors.affiliation: Department of Earth Science and Thomas Young Centre, University College London, London WC1E 6BT, United Kingdom.
authors.forename: Sam
authors.initials: S
authors.lastname: Azadi
authors.affiliation: London Centre for Nanotechnology, University College London, London WC1E 6BT, United Kingdom and Extreme Materials Initiative, Geophysical Laboratory, Carnegie Institution of Washington, Washington, D.C. 20015, USA.
authors.forename: R E
authors.initials: RE
authors.lastname: Cohen
mesh_terms: D001554:Benzene / Q000737:chemistry*; D004058:Diffusion; D019281:Dimerization; D008956:Models, Chemical; D009010:Monte Carlo Method; D011789:Quantum Theory; D055672:Static Electricity
chemical_list: D001554:Benzene