Intermolecular Interaction Energies in Molecular Crystals: Comparison and Agreement of Localized Møller–Plesset 2, Dispersion-Corrected Density Functional, and Classical Empirical Two-Body Calculations

Maschio, Lorenzo; Civalleri, Bartolomeo; Ugliengo, Piero; Gavezzotti, Angelo

doi:10.1021/jp203132k

Cited by 174 publications

(197 citation statements)

References 59 publications

Supporting

Mentioning

186

Contrasting

Order By: Relevance

“…65 Other broad estimates are ±10%. 25 Some of the systems in the present database, such as naphthalene and anthracene, are established thermochemical standards with well-defined uncertainties of around 1-2 kJ/mol. 55 For other systems larger uncertainties, up to 10 kJ/mol, are not uncommon and there can often be a wide variation between different experimental measurements.…”

Section: Overview Of the X23 Databasementioning

confidence: 99%

“…[24][25][26][27] This comparison requires accounting for a number of vibrational contributions. In many instances these contributions were either ignored or considered in the hightemperature limit, whereby following the Dulong-Petit law the relationship reduces to 25,28 A realistic benchmark of DFT methods requires the accurate estimation of the vibrational contributions to the sublimation enthalpy to avoid systematic bias towards methods that over-or underestimate lattice energies. It is equally important to properly assess the role of the density functional used to calculate the lattice energies.…”

Section: Introductionmentioning

confidence: 99%

“…It is equally important to properly assess the role of the density functional used to calculate the lattice energies. While many studies have focused on the role of dispersion, 25,29,30 few have critically assessed the shortcomings of semi-local functionals in detail. For example, the de-localisation or selfinteraction errors in DFT 31 can often have a significant effect on hydrogen-bonded systems.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Reilly

Tkatchenko

2013

The Journal of Chemical Physics

298

498

View full text Add to dashboard Cite

The development and application of computational methods for studying molecular crystals, particularly density-functional theory (DFT), is a large and ever-growing field, driven by their numerous applications. Here we expand on our recent study of the importance of many-body van der Waals interactions in molecular crystals [A. M. Reilly and A. Tkatchenko, J. Phys. Chem. Lett. 4, 1028 (2013)], with a larger database of 23 molecular crystals. Particular attention has been paid to the role of the vibrational contributions that are required to compare experiment sublimation enthalpies with calculated lattice energies, employing both phonon calculations and experimental heat-capacity data to provide harmonic and anharmonic estimates of the vibrational contributions. Exact exchange, which is rarely considered in DFT studies of molecular crystals, is shown to have a significant contribution to lattice energies, systematically improving agreement between theory and experiment. When the vibrational and exact-exchange contributions are coupled with a many-body approach to dispersion, DFT yields a mean absolute error (3.92 kJ/mol) within the coveted "chemical accuracy" target (4.2 kJ/mol). The role of many-body dispersion for structures has also been investigated for a subset of the database, showing good performance compared to X-ray and neutron diffraction crystal structures. The results show that the approach employed here can reach the demanding accuracy of crystal-structure prediction and organic material design with minimal empiricism. © 2013 AIP Publishing LLC. [http://dx

show abstract

Section: Overview Of the X23 Databasementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Reilly

Tkatchenko

2013

The Journal of Chemical Physics

298

498

View full text Add to dashboard Cite

show abstract

“…Nonetheless, the applicability of MP2 to molecular crystals of chemical interest and medium size has been recently carried out 331 as well as recent parallelization of the CRYSCOR code 332 opening the possibility for applications dealing with adsorption of large molecules on silica surfaces.…”

Section: Q(001) Q(010)mentioning

confidence: 99%

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…The counterpoise (CP) corrected cohesive energy per molecule at a given volume V and for a given basis has been computed as 110,111 …”

Section: Benchmark Calculations a Computational Detailsmentioning

confidence: 99%

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Ben

Hutter

VandeVondele

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scalability and efficiency up to thousands of nodes. Additionally, the computationally more demanding quintic scaling steps can be accelerated by employing graphics processing units (GPU's) showing, for large systems, a gain of almost a factor two compared to the standard central processing unit-only case. In this way, the evaluation of the derivatives of the RI-MP2 energy can be performed within a few minutes for systems containing hundreds of atoms and thousands of basis functions. With good time to solution, the implementation thus opens the possibility to perform molecular dynamics (MD) simulations in various ensembles (microcanonical ensemble and isobaric-isothermal ensemble) at the MP2 level of theory. Geometry optimization, full cell relaxation, and energy conserving MD simulations have been performed for a variety of molecular crystals including NH3, CO2, formic acid, and benzene. The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scala...

show abstract

Intermolecular Interaction Energies in Molecular Crystals: Comparison and Agreement of Localized Møller–Plesset 2, Dispersion-Corrected Density Functional, and Classical Empirical Two-Body Calculations

Cited by 174 publications

References 59 publications

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

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

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Contact Info

Product

Resources

About