Ab initio determination of the crystalline benzene lattice energy to sub-kilojoule/mole accuracy

作者：Yang Jun; Hu Weifeng; Usvyat Denis; Matthews Devin; Schuetz Martin; Chan Garnet Kin Lic^*

来源：Science, 2014, 345(6197): 640-643.

DOI：10.1126/science.1254419

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.

• 出版日期2014-8-8