Improving density functional theory for crystal polymorph energetics

Christopher R. Taylor, Peter J. Bygrave, Judy N. Hart, Neil L. Allan, Frederick R. Manby

Research output: Contribution to journalArticle (Academic Journal)peer-review

27 Citations (Scopus)


We show that the quality of density functional theory (DFT) predictions for the relative stabilities of polymorphs of crystalline para-diiodobenzene (PDIB) is dramatically improved through a simple two-body correction using wavefunction-based electronic structure theory. PDIB has two stable polymorphs under ambient conditions, and like Hongo et al. [J. Phys. Chem. Lett., 1, 1789 (2010)] we find that DFT makes wildly variable predictions of the relative stabilities, depending on the approximate functional used. The two-body corrected scheme, using Grimme's spin-scaled variant of second-order Moller-Plesset perturbation theory and any of the tested density functionals, predicts the a-polymorph to be more stable, consistent with experiment, and produces a relative stability that agrees with the benchmark quantum Monte-Carlo results of Hongo et al. within statistical uncertainty.

Original languageEnglish
Pages (from-to)7739-7743
Number of pages5
JournalPhysical Chemistry Chemical Physics
Issue number21
Publication statusPublished - Feb 2012


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