Comment on “Physisorption of Water on Graphene: Subchemical Accuracy from Many-Body Electronic Structure Methods”

Jordan, Kenneth D.; Heßelmann, Andreas

doi:10.1021/acs.jpcc.9b02326

Cited by 12 publications

(16 citation statements)

References 46 publications

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“…We test as many as 28 DFAs on the WaC18 set, including several recently developed vdW corrections to DFAs. Some DFT benchmarks already exist on these or related system types, [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76] but they typically include a limited set of DFAs, the recent vdW developments are not included, and the used reference data is not equally well converged. Here, we will address all of these issues.…”

Section: Introductionmentioning

confidence: 99%

Interaction between water and carbon nanostructures: How good are current density functional approximations?

Brandenburg

Zen

Michaelides

2019

The Journal of Chemical Physics

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Due to their current and future technological applications, including realisation of water filters and desalination membranes, water adsorption on graphitic sp 2 -bonded carbon is of overwhelming interest. However, these systems are notoriously challenging to model, even for electronic structure methods such as density functional theory (DFT), because of the crucial role played by London dispersion forces and non-covalent interactions in general. Recent efforts have established reference quality interactions of several carbon nanostructures interacting with water. Here, we compile a new benchmark set (dubbed WaC18), which includes a single water molecule interacting with a broad range of carbon structures, and various bulk (3D) and two dimensional (2D) ice polymorphs. The performance of 28 approaches, including semi-local exchange-correlation functionals, non-local (Fock) exchange contributions, and long-range van der Waals (vdW) treatments, are tested by computing the deviations from the reference interaction energies. The calculated mean absolute deviations on the WaC18 set depends crucially on the DFT approach, ranging from 135 meV for LDA to 12 meV for PBE0-D4. We find that modern vdW corrections to DFT significantly improve over their precursors. Within the 28 tested approaches, we identify the best performing within the functional classes of: generalized gradient approximated (GGA), meta-GGA, vdW-DF, and hybrid DF, which are BLYP-D4, TPSS-D4, rev-vdW-DF2, and PBE0-D4, respectively.

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Section: Introductionmentioning

confidence: 99%

Interaction between water and carbon nanostructures: How good are current density functional approximations?

Brandenburg

Zen

Michaelides

2019

The Journal of Chemical Physics

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“…Straightforward extrapolations of interactions from small molecules to large complexes are difficult to make due to the interplay and accumulation of interactions that are non-additive, anisotropic, or have many-body character 21,[23][24][25][26] . As such, a deeper understanding of non-covalent interactions can be gained by directly applying state-of-the-art methods in larger molecular complexes.…”

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confidence: 99%

Interactions between large molecules pose a puzzle for reference quantum mechanical methods

et al. 2021

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Quantum-mechanical methods are used for understanding molecular interactions throughout the natural sciences. Quantum diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] are state-of-the-art trusted wavefunction methods that have been shown to yield accurate interaction energies for small organic molecules. These methods provide valuable reference information for widely-used semi-empirical and machine learning potentials, especially where experimental information is scarce. However, agreement for systems beyond small molecules is a crucial remaining milestone for cementing the benchmark accuracy of these methods. We show that CCSD(T) and DMC interaction energies are not consistent for a set of polarizable supramolecules. Whilst there is agreement for some of the complexes, in a few key systems disagreements of up to 8 kcal mol−1 remain. These findings thus indicate that more caution is required when aiming at reproducible non-covalent interactions between extended molecules.

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“…Straightforward extrapolations of interactions from small molecules to large complexes are difficult to make due to the interplay and accumulation of interactions that are non-additive, anisotropic, or have many-body character [11,[19][20][21][22]. As such, a deeper understanding of non-covalent interactions can be gained by directly applying state-of-the-art methods in larger molecular complexes.…”

Section: Mainmentioning

confidence: 99%

Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods

Al-Hamdani,

Nagy,

Barton

et al. 2020

Preprint

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Quantum-mechanical methods are widely used for understanding molecular interactions throughout biology, chemistry, and materials science. Quantum diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] are two state-of-the-art and trusted wavefunction methods that have been categorically shown to yield accurate interaction energies for small organic molecules.These methods provide valuable reference information for widely-used semi-empirical and machine learning potentials, especially where experimental information is scarce. However, agreement for systems beyond small molecules is a crucial remaining milestone for cementing the benchmark accuracy of these methods. Approaching such well-converged predictive power in larger molecules has motivated major developments in CCSD(T) as well as DMC algorithms in the past years, resulting in orders of magnitude time-to-solution reductions. Here, we show that CCSD(T)and DMC interaction energies are not in consistent agreement for a set of polarizable supramolecules. Whilst agreement is found for some of the complexes, in a few key systems disagreements of up to 8 kcal mol −1 remained. This leads to differences of up to 6 orders of magnitude in the corresponding binding association constant at room temperature for systems which are well within the accustomed domain of applicability for both methods. These findings thus indicate that more caution is required when aiming at reproducible non-covalent interactions between extended molecules.Our data contradicts the expectation that the most comprehensive and robust wavefunction methods predict identical non-covalent interactions and indicate an unsolved challenge for benchmark approaches.

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Comment on “Physisorption of Water on Graphene: Subchemical Accuracy from Many-Body Electronic Structure Methods”

Cited by 12 publications

References 46 publications

Interaction between water and carbon nanostructures: How good are current density functional approximations?

Interaction between water and carbon nanostructures: How good are current density functional approximations?

Interactions between large molecules pose a puzzle for reference quantum mechanical methods

Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods

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