Prediction of lattice energy of benzene crystals: a robust theoretical approach

Anh L.P. Nguyen, Thomas G. Mason, Benny D. Freeman, Ekaterina I. Izgorodina

Research output: Contribution to journalArticleResearchpeer-review

Abstract

We present an inexpensive and robust theoretical approach based on the fragment molecular orbital methodology and the spin-ratio scaled second-order Møller–Plesset perturbation theory to predict the lattice energy of benzene crystals within 2 kJ⋅mol−1. Inspired by the Harrison method to estimate the Madelung constant, the proposed approach calculates the lattice energy as a sum of two- and three-body interaction energies between a reference molecule and the surrounding molecules arranged in a sphere. The lattice energy converges rapidly at a radius of 13 Å. Adding the corrections to account for a higher correlated level of theory and basis set superposition for the Hartree Fock (HF) level produced a lattice energy of −57.5 kJ⋅mol−1 for the benzene crystal structure at 138 K. This estimate is within 1.6 kJ⋅mol−1 off the best theoretical prediction of −55.9 kJ⋅mol−1. We applied this approach to calculate lattice energies of the crystal structures of phase I and phase II—polymorphs of benzene—observed at a higher temperature of 295 K. The stability of these polymorphs was correctly predicted, with phase II being energetically preferred by 3.7 kJ⋅mol−1 over phase I. The proposed approach gives a tremendous potential to predict stability of other molecular crystal polymorphs.

Original languageEnglish
Pages (from-to)248-260
Number of pages13
JournalJournal of Computational Chemistry
Volume42
Issue number4
DOIs
Publication statusPublished - 5 Feb 2021

Keywords

  • correlation
  • crystal structure
  • energy
  • energy ab-initio
  • gas-phase

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