Intermolecular Interaction Energies in Molecular Crystals: Comparison and Agreement of Localized Møller–Plesset 2, Dispersion-Corrected Density Functional, and Classical Empirical Two-Body Calculations
- 6 September 2011
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 115 (41), 11179-11186
- https://doi.org/10.1021/jp203132k
Abstract
A comparative analysis of the intermolecular energy for a data set including 60 molecular crystals with a large variety of functional groups has been carried out using three different computational approaches: (i) a method based on a physically meaningful empirical partition of the interaction energy (PIXEL), (ii) density functional methods with a posteriori empirical correction for the dispersion interactions (DFT-D), and (iii) a full periodic ab initio quantum mechanical method based on Møller–Plesset perturbation theory for the electron correlation using localized crystal orbitals (LMP2). Due to the large computational cost, LMP2 calculations have been restricted to a subset of seven molecular crystal comprising benzene, formic acid, formamide, succinic anhydride, urea, oxalic acid, and nitroguanidine, and the results compared with PIXEL and DFT-D data as well as with the experimental data show excellent agreement among all adopted methods. This shows that both DFT-D and PIXEL approaches are robust predictive tools for studying molecular crystals. A detailed analysis shows a very similar dispersion contribution of the two methods across the 60 considered molecular crystals. The study also confirms that pure DFT shows serious deficiencies in properly handling molecular crystals in which the dispersive contribution is large. Due to the negligible requested computational resources, PIXEL is the method of choice in screening of a large number of molecular crystals, an essential step to predict crystal polymorphism or to study crystal growth processes. DFT-D can then be used to refine the ranking emerged from PIXEL calculations due to its general applicability and robustness in properly handling short-range interactions.Keywords
This publication has 54 references indexed in Scilit:
- Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculationsActa crystallographica Section B, Structural science, crystal engineering and materials, 2010
- First-Principles Lattice Energy Calculation of Urea and Hexamine Crystals by a Combination of Periodic DFT and MP2 Two-Body Interaction Energy CalculationsThe Journal of Physical Chemistry B, 2010
- Layered crystal structure of bicyclic aziridines as revealed by analysis of intermolecular interactions energyCrystEngComm, 2010
- Structures and Aggregation of the Methylamine−Borane Molecules, MenH3−nN·BH3(n= 1−3), Studied by X-ray Diffraction, Gas-Phase Electron Diffraction, and Quantum Chemical CalculationsJournal of the American Chemical Society, 2009
- The Anisotropic Compression of the Crystal Structure of 3-Aza-bicyclo(3.3.1)nonane-2,4-dione to 7.1 GPaCrystal Growth & Design, 2008
- B3LYP augmented with an empirical dispersion term (B3LYP-D*) as applied to molecular crystalsCrystEngComm, 2007
- Accurate ab Initio Binding Energies of the Benzene DimerThe Journal of Physical Chemistry A, 2006
- Calculation of Intermolecular Interaction Energies by Direct Numerical Integration over Electron Densities. I. Electrostatic and Polarization Energies in Molecular CrystalsThe Journal of Physical Chemistry B, 2002
- Structure de l'α-naphtoquinoneActa Crystallographica, 1965
- Über das Verhältnis der van der Waalsschen Kräfte zu den homöopolaren BindungskräftenThe European Physical Journal A, 1930