Quantum Monte Carlo for Noncovalent Interactions: An Efficient Protocol Attaining Benchmark Accuracy

Abstract

Reliable theoretical predictions of noncovalent interaction energies, which are important e.g. in drug-design and hydrogen-storage applications, belong to longstanding challenges of contemporary quantum chemistry. In this respect, the fixed-node diffusion Monte Carlo (FN-DMC) is a promising alternative to the commonly used "gold standard" coupled-cluster CCSD(T)/CBS method for its benchmark accuracy and favourable scaling, in contrast to other correlated wave function approaches. This work is focused on the analysis of protocols and possible tradeoffs for FN-DMC estimations of noncovalent interaction energies and proposes an efficient yet accurate computational protocol using simplified explicit correlation terms with a favorable O(N^3) scaling. It achieves an excellent agreement (mean unsigned error ~0.2 kcal/mol) with respect to the CCSD(T)/CBS data on a number of complexes, including benzene/hydrogen,T-shape benzene dimer, stacked adenine-thymine and a set of small noncovalent complexes A24. The high accuracy and reduced computational costs predestinate the reported protocol for practical interaction energy calculations of large noncovalent complexes, where the CCSD(T)/CBS is prohibitively expensive.

References in corpus (11)

• Continuum variational and diffusion quantum Monte Carlo calculations
• On the accuracy of DFT exchange-correlation functionals for H bonds in small water clusters II: The water hexamer and van der Waals interactions
• Beyond the locality approximation in the standard diffusion Monte Carlo method
• Energy and variance optimization of many body wave functions
• A variance-minimization scheme for optimizing Jastrow factors
• Optimized Jastrow-Slater wave functions for ground and excited states: Application to the lowest states of ethene
• Approaching Chemical Accuracy with Quantum Monte Carlo
• Wave functions for quantum Monte Carlo calculations in solids: Orbitals from density functional theory with hybrid exchange-correlation functionals
• Molecular properties by Quantum Monte Carlo: an investigation on the role of the wave function ansatz and the basis set in the water molecule
• Molecular hydrogen adsorbed on benzene: insights from a quantum Monte Carlo study
• Fixed-node errors in quantum Monte Carlo: interplay of electron density and node nonlinearities

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