Article (Scientific journals)
Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals
Reilly, Anthony M.; Tkatchenko, Alexandre
2013In Journal of Chemical Physics, 139 (2)
Peer reviewed
 

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Keywords :
Development and applications; Many-body approach; Mean absolute error; Phonon calculation; Sublimation enthalpy; Van Der Waals interactions; Vibrational contributions; X-Ray and neutron diffraction; Crystal structure; Design for testability; Dispersions; Experiments; Lattice theory; Neutron diffraction; Van der Waals forces; Molecular crystals
Abstract :
[en] The development and application of computational methods for studying molecular crystals, particularly density-functional theory (DFT), is a large and ever-growing field, driven by their numerous applications. Here we expand on our recent study of the importance of many-body van der Waals interactions in molecular crystals [A. M. Reilly and A. Tkatchenko, J. Phys. Chem. Lett. 4, 1028 (2013)], with a larger database of 23 molecular crystals. Particular attention has been paid to the role of the vibrational contributions that are required to compare experiment sublimation enthalpies with calculated lattice energies, employing both phonon calculations and experimental heat-capacity data to provide harmonic and anharmonic estimates of the vibrational contributions. Exact exchange, which is rarely considered in DFT studies of molecular crystals, is shown to have a significant contribution to lattice energies, systematically improving agreement between theory and experiment. When the vibrational and exact-exchange contributions are coupled with a many-body approach to dispersion, DFT yields a mean absolute error (3.92 kJ/mol) within the coveted "chemical accuracy" target (4.2 kJ/mol). The role of many-body dispersion for structures has also been investigated for a subset of the database, showing good performance compared to X-ray and neutron diffraction crystal structures. The results show that the approach employed here can reach the demanding accuracy of crystal-structure prediction and organic material design with minimal empiricism. © 2013 AIP Publishing LLC.
Disciplines :
Physics
Identifiers :
eid=2-s2.0-84903362397
Author, co-author :
Reilly, Anthony M.;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Tkatchenko, Alexandre ;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
External co-authors :
yes
Title :
Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals
Publication date :
2013
Journal title :
Journal of Chemical Physics
ISSN :
0021-9606
Volume :
139
Issue :
2
Peer reviewed :
Peer reviewed
Funders :
VDW-CMAT, ERC, European Research Council
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