@article{324cea7169d94583b8a47fb7d3e6de29,
title = "Powder diffraction and crystal structure prediction identify four new coumarin polymorphs",
abstract = "Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and the need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.",
author = "Shtukenberg, {Alexander G.} and Qiang Zhu and Carter, {Damien J.} and Leslie Vogt and Johannes Hoja and Elia Schneider and Hongxing Song and Boaz Pokroy and Iryna Polishchuk and Alexandre Tkatchenko and Oganov, {Artem R.} and Rohl, {Andrew L.} and Tuckerman, {Mark E.} and Bart Kahr",
note = "Funding Information: This work was primarily supported by the New York University Materials Research Science and Engineering Center (MRSEC) program of the National Science Foundation under award number DMR-1420073, and the National Nuclear Security Administration under the Stewardship Science Academic Alliances program through DOE Cooperative Agreement DE-NA0001982. Funding support was also provided by the National Science Foundation (grant DMR-1608374), Australian Research Council (grant DP140101776) and the Army Research Office (ARO) in the form of a Multidisciplinary University Research Initiative (MURI) (grant W911NF-13-1-0387) for L. V. B. P. acknowledges the funding received from the European Research Council under the European Union's Seventh Framework Program (FP/2007-2013)/ERC Grant Agreement (no. 336077). This work was supported by computational resources provided by XSEDE facilities, Center for Functional Nanomaterials under contract no. DE-AC02-98CH10086, the Australian Government through the Pawsey Centre under the National Computational Merit Allocation Scheme, and High Performance Computing resources at New York University. The authors acknowledge Dr Chunhua Hu (NYU Department of Chemistry X-ray Diffraction Facility) and the NSF Chemistry Research Instrumentation and Facilities Program (CHE-0840277) for the powder microdiffractometer. The high-resolution powder diffraction measurements were performed on beamline ID22 at the European Synchrotron Radiation Facility (ESRF), Grenoble, France during experiments CH 4328 and MA 2916. We are grateful to Dr Carlotta Giacobbe for providing assistance in using the beamline as well as Dr Eva Weber and Maria Koifman for their assistance in data collection. Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",
year = "2017",
doi = "10.1039/c7sc00168a",
language = "English (US)",
volume = "8",
pages = "4926--4940",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "7",
}