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Published August 8, 2014 | metadata_only
Journal Article

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


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.

Additional Information

© 2014, American Association for the Advancement of Science. 4 April 2014; accepted 8 July 2014. We acknowledge many helpful discussions with C. D. Sherrill, G. J. O. Beran, and R. Podeszwa. We especially thank R. Podeszwa for providing the detailed data on dimer and trimer geometries and A. Tkatchenko for providing unpublished ZPE data. Work performed by J.Y., W.H., and G.K.-L.C. was supported by the U.S. Department of Energy under grant no. DE-SC0008624, with secondary support from grant no. DE-SC0010530. The DMRG software package BLOCK used in part of this work was developed with primary funding from NSF grant no. OCI-1265278. BLOCK implements theoretical methods developed under NSF grant no. CHE-1265277. D.M. was supported by the U.S. Department of Energy through a Computational Science Graduate Fellowship, funded by grant no. DE-FG02-7ER25308. D.U. and M.S. acknowledge financial support from the Deutsche Forschungsgemeinschaft (DFG), grants US-103/1-1 and SCHU 1456/12-1.

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August 20, 2023
August 20, 2023