Benchmarking several van der Waals dispersion approaches for the description of intermolecular interactions

Claudot, Julien; Kim, Won June; Dixit, Anant; Kim, Hyungjun; Gould, Tim; Rocca, Dario; Lebègue, Sébastien

doi:10.1063/1.5018818

Cited by 39 publications

(24 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This result is consistent with our recent comparison of van der Waals functionals in broader contexts [41]. Tables IV and V depict how the 12 computational methods not involving hybrid functionals fare in terms of predicting observed properties of CuInP 2 S 6 and CuBiP 2 Se 6 crystals.…”

Section: Pbe-scsts and Pbe-mbd@rsscssupporting

confidence: 87%

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆

et al. 2018

View full text Add to dashboard Cite

Following the recent demonstration that van der Waals forces control the ferroelectric ordering of layers within nanoflakes and bulk samples of CuBiP 2 Se 6 and CuInP 2 S 6 , it is demonstrated that they also control the internal geometrical structure of isolated monolayers of these materials. This internal structure involves large displacements of the copper atoms, either normal to the layer plane or else within the plane, that change its ligation environment. In both cases, the van der Waals dispersion force out-competes traditional bonding effects to control structure. However, we find that the aspects of the dispersion force giving rise to each effect are uncorrelated: long range effects control interlayer ferroelectric ordering whereas short-range effects control internal layer structure. These conclusions are drawn considering predicted properties of monolayers, bilayers, and bulk materials obtained using 14 density-functional-theory based methods. While the different methods used often predict starkly different quantitative results, they concur as to the basic nature of ABP 2 X 6 materials. Of the methods used, only the PBE-D3 and optPBEvdW methods were found to predict a wide range of observed properties without serious disparity.Finding optimal computational methods remains a significant challenge for which the unusual multi-scale nature of the van der Waals interactions in ABP 2 X 6 materials provides demanding criteria. PACSNumbers 31.13.E dft or 31.15.eg functionals 68.65.ac multilayers

show abstract

Section: Pbe-scsts and Pbe-mbd@rsscssupporting

confidence: 87%

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆

et al. 2018

View full text Add to dashboard Cite

show abstract

“…In particular, the increase in the number of hydrogen bonds in the L7 dataset could be challenging for DFT approximations 154 . This is demonstrated in the recent work of Claudot et al 69 where the L7 dataset was benchmarked with several vdW inclusive xc functionals and significant discrepancies were found for hydrogen-bonded complexes. It has previously been shown, for example, that predicting the electrostatic interactions can require a more accurate description of Pauli exchange-repulsion, 70,154 and therefore in the realm of DFT xc functionals, more expensive hybrid functionals might be needed to accurately compute the L7 dataset.…”

Section: The Dft Workhorse On a Complex Molecular Trackmentioning

confidence: 99%

Understanding non-covalent interactions in larger molecular complexes from first principles

Al-Hamdani

Tkatchenko

2019

The Journal of Chemical Physics

138

View full text Add to dashboard Cite

Non-covalent interactions pervade all matter and play a fundamental role in layered materials, biological systems, and large molecular complexes. Despite this, our accumulated understanding of non-covalent interactions to date has been mainly developed in the tens-of-atoms molecular regime. This falls considerably short of the scales at which we would like to understand energy trends, structural properties, and temperature dependencies in materials where non-covalent interactions have an appreciable role. However, as more reference information is obtained beyond moderately sized molecular systems, our understanding is improving and we stand to gain pertinent insights by tackling more complex systems, such as supramolecular complexes, molecular crystals, and other soft materials. In addition, accurate reference information is needed to provide the drive for extending the predictive power of more efficient workhorse methods, such as density functional approximations that also approximate van der Waals dispersion interactions. In this perspective, we discuss the first-principles approaches that have been used to obtain reference interaction energies for beyond modestly sized molecular complexes. The methods include quantum Monte Carlo, symmetry-adapted perturbation theory, non-canonical coupled cluster theory, and approaches based on the random-phase approximation. By considering the approximations that underpin each method, the most accurate theoretical references for supramolecular complexes and molecular crystals to date are ascertained. With these, we also assess a handful of widely used exchange-correlation functionals in density functional theory. The discussion culminates in a framework for putting into perspective the accuracy of high-level wavefunction-based methods and identifying future challenges.

show abstract

“…[33] Harmonic B3LYP-D3(BJ) calculations show high predictive power for the spectroscopic chirality recognition, while M06-2X, wB97X-D,and AM1 do not. It is not clear how chirality-induced spin selectivity [3] modulates these spectral shifts,but model calculations are invited, as are calculations using alternative density functionals, [34,35] to see whether they perform even better than B3LYP-D3(BJ).…”

Section: Communicationsmentioning

confidence: 99%

Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking

2019

View full text Add to dashboard Cite

Chirality recognition between largely rigid molecules can be applied as ab enchmark for the description of intermolecular forces by theoretical methods,b ecause one constituent is merely mirrored, so other deficits of the methods such as neglect of anharmonicity should mostly cancel. To test this approach, mixed OH···p-bridged dimers between the enantiomers of the bicyclic monoterpene a-pinene and the chiral secondary alcohols borneol, a-fenchol, isopinocampheol, and 1-phenylethanol were formed in as upersonic jet and probed by linear FTIR spectroscopy. With borneol and afenchol, pronounced shifts in the hydroxyl stretching frequencies upon exchange of the handedness are observed. From three tested density functionals,only B3LYP-D3(BJ) is able to predict these diastereomeric shifts in as atisfactory manner, while M06-2X and wB97X-D fall short.Chirality recognition, the ability of chiral objects to distin-Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

show abstract

Benchmarking several van der Waals dispersion approaches for the description of intermolecular interactions

Cited by 39 publications

References 75 publications

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆

Understanding non-covalent interactions in larger molecular complexes from first principles

Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking

Contact Info

Product

Resources

About

Benchmarking several van der Waals dispersion approaches for the description of intermolecular interactions

Cited by 39 publications

References 75 publications

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP2S6 and CuBiP2Se6

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP2S6 and CuBiP2Se6

Understanding non-covalent interactions in larger molecular complexes from first principles

Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking

Contact Info

Product

Resources

About

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆

van der Waals Forces Control the Internal Chemical Structure of Monolayers within the Lamellar Materials CuInP₂S₆ and CuBiP₂Se₆