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 (15)

• Van der Waals Density Functional for General Geometries
• Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
• Generalized Lanczos Algorithm for Variational Quantum Monte Carlo
• Wave function optimization in the variational Monte Carlo method
• 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
• Correlated geminal wave function for molecules: an efficient resonating valence bond approach
• Geminal wavefunctions with Jastrow correlation: a first application to atoms
• Energy and variance optimization of many body wave functions
• Diffusion Monte Carlo with lattice regularization
• Backflow Correlations for the Electron Gas and Metallic Hydrogen
• Proof for an upper bound in fixed-node Monte Carlo for lattice fermions
• Sharp regularity results for many-electron wave functions
• Energetics and Dipole Moment of Transition Metal Monoxides by Quantum Monte Carlo
• Transition metal oxides using quantum Monte Carlo

Cited by in corpus (14)

• Resonating valence bond wave function with molecular orbitals: Application to first-row molecules
• TurboRVB: a many-body toolkit for {\it ab initio} electronic simulations by quantum Monte Carlo
• Quantum Monte Carlo for Noncovalent Interactions: An Efficient Protocol Attaining Benchmark Accuracy
• Ab-initio calculations for the beta-tin diamond transition in Silicon: comparing theories with experiments
• Self-healing diffusion quantum Monte Carlo algorithms: methods for direct reduction of the fermion sign error in electronic structure calculations
• A hybrid approach to excited-state-specific variational Monte Carlo and doubly excited states
• Complementary First and Second Derivative Methods for Ansatz Optimization in Variational Monte Carlo
• Theory of melting at high pressures: Amending Density Functional Theory with Quantum Monte Carlo
• An accelerated linear method for optimizing non-linear wavefunctions in variational Monte Carlo
• Quantum Monte Carlo Calculations of Dihydrogen Binding Energetics on Ca Cations: an Assessment of Errors in Density Functionals for Weakly Bonded Systems
• Properties of Reactive Oxygen Species by Quantum Monte Carlo
• Quantum Monte Carlo calculated potential energy curve for the helium dimer
• Basis set incompleteness errors in fixed-node diffusion Monte Carlo calculations on non-covalent interactions
• Calculation of the molecular integrals with the range-separated correlation factor