Random Phase Approximation Applied to Many-Body Noncovalent Systems

Abstract

The random phase approximation (RPA) has received a considerable interest in the field of modeling systems where noncovalent interactions are important. Its advantages over widely used density functional theory (DFT) approximations are the exact treatment of exchange and the description of long-range correlation. In this work we address two open questions related to RPA. First, how accurately RPA describes nonadditive interactions encountered in many-body expansion of a binding energy. We consider three-body nonadditive energies in molecular and atomic clusters. Second, how does the accuracy of RPA depend on input provided by different DFT models, without resorting to selfconsistent RPA procedure which is currently impractical for calculations employing periodic boundary conditions. We find that RPA based on the SCAN0 and PBE0 models, i.e., hybrid DFT, achieves an overall accuracy between CCSD and MP3 on a dataset of molecular trimers of Řezáč et al. (J. Chem. Theory. Comput. 2015, 11, 3065) Finally, many-body expansion for molecular clusters and solids often leads to a large number of small contributions that need to be calculated with a high precision. We therefore present a cubic-scaling (or SCF-like) implementation of RPA in atomic basis set, which is designed for calculations with a high numerical precision.

References in corpus (24)

• Phonons and related properties of extended systems from density-functional perturbation theory
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• A Higher-Accuracy van der Waals Density Functional
• Nonlocal van der Waals density functional: The simpler the better
• Perspective: How good is DFT for water?
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• Long-range correlation energy calculated from coupled atomic response functions
• Beyond the Random Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations
• Reliable and Practical Computational Prediction of Molecular Crystal Polymorphs
• SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters
• The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes
• On the physisorption of water on graphene: Sub-chemical accuracy from many-body electronic structure methods
• Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory
• Fast and accurate quantum Monte Carlo for molecular crystals
• Energy benchmarks for water clusters and ice structures from an embedded many-body expansion
• Properties of the water to boron nitride interaction: from zero to two dimensions with benchmark accuracy
• Singles correlation energy contributions in solids
• Beyond the random phase approximation with a local exchange vertex
• Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation
• Lattice energies of molecular solids from the random phase approximation with singles corrections
• The nature of three-body interactions in DFT: exchange and polarization effects
• Transition properties from the Hermitian formulation of the coupled cluster polarization propagator
• Transition moments between excited electronic states from the Hermitian formulation of the coupled cluster quadratic response function
• Renormalized Second-order Perturbation Theory for The Electron Correlation Energy: Concept, Implementation, and Benchmarks

Cited by in corpus (7)

• Efficient and accurate description of adsorption in zeolites
• Towards Pair Atomic Density Fitting for Correlation Energies with Benchmark Accuracy
• Assessment of the second-order statically screened exchange correction to the random phase approximation for correlation energies
• Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage
• Assessment of random-phase approximation and second order Møller-Plesset perturbation theory for many-body interactions in solid ethane, ethylene, and acetylene
• Tensor hypercontraction for fully self-consistent imaginary-time GF2 and GWSOX methods: theory, implementation, and role of the Green's function second-order exchange for intermolecular interactions
• Understanding the wetting of transition metal dichalcogenides from an ab initio perspective