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 0.18 mHa, suggesting 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. We compare with empirical models and previous calculations, and we discuss the physical mechanisms of the interaction, the role of diffuse basis functions, and the charge redistribution in the bond.

12 pages, 4 figures

References in corpus (4)

• Weak binding between two aromatic rings: feeling the van der Waals attraction by quantum Monte Carlo methods
• Beyond the locality approximation in the standard diffusion Monte Carlo method
• Energetics and Dipole Moment of Transition Metal Monoxides by Quantum Monte Carlo
• Transition metal oxides using quantum Monte Carlo

Cited by in corpus (1)

• Resonating valence bond wave function with molecular orbitals: Application to first-row molecules