Accurate and Efficient Model Energies for Exploring Intermolecular Interactions in Molecular Crystals

Turner, Michael J.; Grabowsky, Simon; Jayatilaka, Dylan; Spackman, Mark A. (2014). Accurate and Efficient Model Energies for Exploring Intermolecular Interactions in Molecular Crystals. The journal of physical chemistry letters, 5(24), pp. 4249-4255. American Chemical Society 10.1021/jz502271c

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The energy of interaction between molecules is commonly expressed in terms of four key components: electrostatic, polarization, dispersion, and exchange-repulsion. Using monomer wave functions to obtain accurate estimates of electrostatic, polarization, and repulsion energies along with Grimme’s dispersion corrections, a series of energy models are derived by fitting to dispersion-corrected DFT energies for a large number of molecular pairs extracted from organic and inorganic molecular crystals. The best performing model reproduces B3LYP-D2/6-31G(d,p) counterpoise-corrected energies with a mean absolute deviation (MAD) of just over 1 kJ mol–1 but in considerably less computation time. It also performs surprisingly well against benchmark CCSD(T)/CBS energies, with a MAD of 2.5 kJ mol–1 for a combined data set including Hobza’s X40, S22, A24, and S66 dimers. Two of these energy models, the most accurate and the fastest, are expected to find widespread application in investigations of molecular crystals.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Grabowsky, Simon


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry




American Chemical Society




Simon Grabowsky

Date Deposited:

06 Feb 2020 11:59

Last Modified:

05 Dec 2022 15:35

Publisher DOI:





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