Toward a Reliable Description of the Lattice Vibrations in Organic Molecular Crystals: The Impact of van der Waals Interactions

Natalia Bedoya-Martínez, Andrea Giunchi, Tommaso Salzillo, Elisabetta Venuti, Raffaele Guido Della Valle, Egbert Zojer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

This work assesses the reliability of different van der Waals (vdW) methods to describe lattice vibrations of molecular crystals in the framework of density functional theory (DFT). To accomplish this task, calculated and experimental lattice phonon Raman spectra of a pool of organic molecular crystals are compared. We show that the many-body dispersion (MBD@rsSCS) van der Waals method of Ambrosetti et al. and the pairwise method of Grimme et al. (D3-BJ) outperform the other tested approaches (i.e., the D2 method of Grimme, the TS method of Tkatchenko and Scheffler, and the nonlocal functional vdW-DF-optPBE of Klimeš et al.). For the worse-performing approaches the results could not even be fixed by the introduction of scaling parameters, as commonly used for high-energy intramolecular vibrations. Interestingly, when using the experimentally determined unit cell parameters, DFT calculations using the PBE functional without corrections for long-range vdW interactions provide spectra of similar accuracy as the MBD@rsSCS and D3-BJ simulations.

Original languageEnglish
Pages (from-to)4380-4390
Number of pages11
JournalJournal of chemical theory and computation
Volume14
Issue number8
DOIs
Publication statusPublished - 14 Aug 2018

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Molecular crystals
Lattice vibrations
lattice vibrations
Density functional theory
density functional theory
deuterium fluorides
crystals
Raman scattering
interactions
Raman spectra
scaling
vibration
cells
simulation
energy

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Fields of Expertise

  • Advanced Materials Science

Cite this

Toward a Reliable Description of the Lattice Vibrations in Organic Molecular Crystals : The Impact of van der Waals Interactions. / Bedoya-Martínez, Natalia; Giunchi, Andrea; Salzillo, Tommaso; Venuti, Elisabetta; Della Valle, Raffaele Guido; Zojer, Egbert.

In: Journal of chemical theory and computation, Vol. 14, No. 8, 14.08.2018, p. 4380-4390.

Research output: Contribution to journalArticleResearchpeer-review

Bedoya-Martínez, Natalia ; Giunchi, Andrea ; Salzillo, Tommaso ; Venuti, Elisabetta ; Della Valle, Raffaele Guido ; Zojer, Egbert. / Toward a Reliable Description of the Lattice Vibrations in Organic Molecular Crystals : The Impact of van der Waals Interactions. In: Journal of chemical theory and computation. 2018 ; Vol. 14, No. 8. pp. 4380-4390.
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