title: Theoretical chemistry. Ab initio determination of the crystalline benzene lattice energy to sub-kilojoule/mole accuracy.
abstract: Computation of lattice energies to an accuracy sufficient to distinguish polymorphs is a fundamental bottleneck in crystal structure prediction. For the lattice energy of the prototypical benzene crystal, we combined the quantum chemical advances of the last decade to attain sub-kilojoule per mole accuracy, an order-of-magnitude improvement in certainty over prior calculations that necessitates revision of the experimental extrapolation to 0 kelvin. Our computations reveal the nature of binding by improving on previously inaccessible or inaccurate multibody and many-electron contributions and provide revised estimates of the effects of temperature, vibrations, and relaxation. Our demonstration raises prospects for definitive first-principles resolution of competing polymorphs in molecular crystal structure prediction.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Jun
authors.initials: J
authors.lastname: Yang
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
authors.forename: Weifeng
authors.initials: W
authors.lastname: Hu
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Regensburg D-93040, Germany.
authors.forename: Denis
authors.initials: D
authors.lastname: Usvyat
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX 078712, USA.
authors.forename: Devin
authors.initials: D
authors.lastname: Matthews
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Regensburg D-93040, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Schütz
authors.affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA. gkchan@princeton.edu.
authors.forename: Garnet Kin-Lic
authors.initials: GK
authors.lastname: Chan