Benchmarking DFT methods with small basis sets for the calculation of halogen-bond strengths

Antti Siiskonen, Arri Priimägi

    Research output: Contribution to journalArticleScientificpeer-review

    15 Citations (Scopus)
    9 Downloads (Pure)


    In recent years, halogen bonding has become an important design tool in crystal engineering, supramolecular chemistry and biosciences. The fundamentals of halogen bonding have been studied extensively with high-accuracy computational methods. Due to its non-covalency, the use of triple-zeta (or larger) basis sets is often recommended when studying halogen bonding. However, in the large systems often encountered in supramolecular chemistry and biosciences, large basis sets can make the calculations far too slow. Therefore, small basis sets, which would combine high computational speed and high accuracy, are in great demand. This study focuses on comparing how well density functional theory (DFT) methods employing small, double-zeta basis sets can estimate halogen-bond strengths. Several methods with triple-zeta basis sets are included for comparison. Altogether, 46 DFT methods were tested using two data sets of 18 and 33 halogen-bonded complexes for which the complexation energies have been previously calculated with the high-accuracy CCSD(T)/CBS method. The DGDZVP basis set performed far better than other double-zeta basis sets, and it even outperformed the triple-zeta basis sets. Due to its small size, it is well-suited to studying halogen bonding in large systems.

    Original languageEnglish
    Article number50
    JournalJournal of Molecular Modeling
    Issue number2
    Publication statusPublished - 1 Feb 2017
    Publication typeA1 Journal article-refereed


    • Basis set
    • Benchmarking
    • Density functional theory
    • Halogen bonding

    Publication forum classification

    • Publication forum level 1

    ASJC Scopus subject areas

    • Catalysis
    • Computer Science Applications
    • Physical and Theoretical Chemistry
    • Organic Chemistry
    • Computational Theory and Mathematics
    • Inorganic Chemistry

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