Systematic discrepancies between reference methods for non-covalent interactions within the S66 dataset
arXiv:2412.16405 · doi:10.1063/5.0254021
Abstract
The accurate treatment of non-covalent interactions is necessary to model a wide range of applications, from molecular crystals to surface catalysts to aqueous solutions and many more. Quantum diffusion Monte Carlo (DMC) and coupled cluster theory with single, double and perturbative triple excitations [CCSD(T)] are considered two widely-trusted methods for treating non-covalent interactions. However, while they have been well-validated for small molecules, recent work has indicated that these two methods can disagree by more than 7.5 kcal/mol for larger systems. The origin of this discrepancy remains unknown. Moreover, the lack of systematic comparisons, particularly for medium-sized complexes, has made it difficult to identify which systems may be prone to such disagreements and the potential scale of these differences. In this work, we leverage the latest developments in DMC to compute interaction energies for the entire S66 dataset, containing 66 medium-sized complexes with a balanced representation of dispersion and electrostatic interactions. Comparison to previous CCSD(T) references reveals systematic trends, with DMC predicting stronger binding than CCSD(T) for electrostatic-dominated systems, while the binding becomes weaker for dispersion-dominated systems. We show that the relative strength of this discrepancy is correlated to the ratio of electrostatic and dispersion interactions, as obtained from energy decomposition analysis methods. Finally, we have pinpointed model systems: the hydrogen-bonded acetic acid dimer (ID 20) and dispersion-dominated uracil-cyclopentane dimer (ID 42), where these discrepancies are particularly prominent. These systems offer cost-effective benchmarks to guide future developments in DMC, CCSD(T) as well as the wider electronic structure theory community.
References in corpus (33)
- Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
- Quantum ESPRESSO toward the exascale
- SCAN+rVV10: A promising van der Waals density functional
- Quantum Monte Carlo Calculation of the Binding Energy of Bilayer Graphene
- r2SCAN-D4: Dispersion corrected meta-generalized gradient approximation for general chemical applications
- An efficient localized basis set for quantum Monte Carlo calculations on condensed matter
- Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods
- QMCPACK: Advances in the development, efficiency, and application of auxiliary field and real-space variational and diffusion Quantum Monte Carlo
- Variational and Diffusion Quantum Monte Carlo Calculations with the CASINO Code
- On the physisorption of water on graphene: Sub-chemical accuracy from many-body electronic structure methods
- A New Generation of Effective Core Potentials for Correlated Calculations
- Fast and accurate quantum Monte Carlo for molecular crystals
- New generation of effective core potentials from correlated calculations: 3d transition metal series
- Boosting the accuracy and speed of quantum Monte Carlo: size-consistency and time-step
- New generation of effective core potentials from correlated calculations: 2nd row elements
- TurboRVB: a many-body toolkit for {\it ab initio} electronic simulations by quantum Monte Carlo
- Properties of the water to boron nitride interaction: from zero to two dimensions with benchmark accuracy
- Shape and Energy Consistent Pseudopotentials for Correlated Electron systems
- How strongly do hydrogen and water molecules stick to carbon nanomaterials?
- A comparison between quantum chemistry and quantum Monte Carlo techniques for the adsorption of water on the (001) LiH surface
- The S66 noncovalent interactions benchmark reconsidered using explicitly correlated methods near the basis set limit
- A new scheme for fixed node diffusion quantum Monte Carlo with pseudopotentials: improving reproducibility and reducing the trial-wave-function bias
- S66x8 Noncovalent Interactions Revisited: New Benchmark and Performance of Composite Localized Coupled-Cluster Methods
- Averting the infrared catastrophe in the gold standard of quantum chemistry
- How accurate are simulations and experiments for the lattice energies of molecular crystals?
- DMC-ICE13: ambient and high pressure polymorphs of ice from Diffusion Monte Carlo and Density Functional Theory
- Periodic Local Coupled-Cluster Theory for Insulators and Metals
- Prototypical pi-pi dimers re-examined by means of high-level CCSDT(Q) composite ab inito methods
- Another Angle on Benchmarking Noncovalent Interactions
- TurboGenius: Python suite for high-throughput calculations of ab initio quantum Monte Carlo methods
- Post-CCSD(T) corrections in the S66 noncovalent interactions benchmark
- Towards chemical accuracy using the Jastrow correlated antisymmetrized geminal power ansatz
- The S66 Noncovalent Interaction Benchmark Re-examined: Composite Localized Coupled Cluster Approaches