Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals

Reilly, Anthony M.; Tkatchenko, Alexandre

doi:10.1063/1.4812819

Cited by 293 publications

(533 citation statements)

References 91 publications

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“…63 An estimate of 4.8 kJ/mol was obtained using DFT many-body dispersion method. 64 This ZPE is significantly larger than an estimate of 2.8 kJ/mol which is obtained by finite molecular cluster calculations. 12,65 Our ZPE results are close to PBC-DFT calculations, 66 where an estimate of 2.6 kJ/mol is obtained using the PBE functional.…”

Section: B Ground State Dft Phase Diagrammentioning

confidence: 58%

Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

Azadi

Cohen

2016

The Journal of Chemical Physics

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We studied the low-pressure (0–10 GPa) phase diagram of crystalline benzene using quantum Monte Carlo and density functional theory (DFT) methods. We performed diffusion quantum Monte Carlo (DMC) calculations to obtain accurate static phase diagrams as benchmarks for modern van der Waals density functionals. Using density functional perturbation theory, we computed the phonon contributions to the free energies. Our DFT enthalpy-pressure phase diagrams indicate that the Pbca and P21/c structures are the most stable phases within the studied pressure range. The DMC Gibbs free-energy calculations predict that the room temperature Pbca to P21/c phase transition occurs at 2.1(1) GPa. This prediction is consistent with available experimental results at room temperature. Our DMC calculations give 50.6 ± 0.5 kJ/mol for crystalline benzene lattice energy

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Section: B Ground State Dft Phase Diagrammentioning

confidence: 58%

Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

Azadi

Cohen

2016

The Journal of Chemical Physics

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“…The common method of deriving these energies from experimental sublimation enthalpies involves several approximations, the particular choice of which can lead to differences as large as 1 kcal/mol. 240,253 In contrast, Yang et al recently calculated the lattice energy of a benzene crystal at the CCSD(T) level with an estimated uncertainty of only ∼0.1 kcal/mol, 295 which may mark a future path toward obtaining suitably accurate benchmark energetics for molecular crystals. Finally, the S12L data set is a difficult problem due to the sheer size of the complexes in question and the fact that they have not been isolated experimentally in the gas phase.…”

Section: Benchmark Databasesmentioning

confidence: 99%

“…Essentially all pairwise methods (D3, XDM, TS) can be made accurate enough for the X23 database by adjusting two empirical parameters. 253 However, such adjustments just serve the purpose of mimicking some of the dielectric screening effects and can only be successful for relatively symmetric systems. The true nature of dielectric screening in arbitrary systems and geometries can only be captured with explicit many-body approaches.…”

Section: Benchmark Databasesmentioning

confidence: 99%

“…The X23 database contains two polymorphs of oxalic acid, for which the experimental energy difference between the α and β forms amounts to only 0.05 kcal/mol. 240,253,279 Yet, current vdW-inclusive first-principle approaches yield energy differences between about −1 and 1 kcal/mol. PBE+MBD has an absolute error in the difference of only 0.12 kcal/mol but predicts the wrong ordering, 7 whereas PBE0+MBD correctly predicts the ordering with an absolute error of 0.22 kcal/mol, illustrating how subtle the differences in the two polymorphs are.…”

Section: Benchmark Databasesmentioning

confidence: 99%

“…The benchmark C21 database 240 extends the analysis to condensed-phase systems via 21 molecular crystals with reference binding energies obtained from experimental sublimation enthalpies. This work was later extended and refined to cover 23 molecular crystals in the X23 database, 253 with a median number of atoms per molecule of 10, molar mass Chemical Reviews of 89 g/mol, and binding energy of 7.3 kcal/mol. The final database considered in this section, the S12L set, deals with large molecules and consists of 12 supramolecular complexes with a median number of atoms of 134, molar mass of 1060 g/mol, and binding energy of 28 kcal/mol, with reference binding energies obtained from experimental Gibbs free energies of association, or alternatively from quantum Monte Carlo calculations.…”

Section: Benchmark Databasesmentioning

confidence: 99%

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First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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