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Accurate modeling of molecular crystal through dispersion-corrected density functional theory (DFT-D) method

Published online by Cambridge University Press:  21 March 2011

Bohdan Schatschneider
Affiliation:
The Pennsylvania State University, Fayette-The Eberly Campus
Jian-jie Liang
Affiliation:
Accelrys, Inc., 10188 Telesis Court, Suite 100 San Diego, CA 92121 USA
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Abstract

Crystal structure, pressure response, and polymorph transformation were investigated for crystalline indole through dispersion-corrected density functional theory (DFT-D) method. An accurate, nonempirical method (as in the latest implementations of CASTEP) is used to correct for the general DFT scheme to include van der Waals interactions important in molecular crystals. Ambient structural details, including space group symmetry, density, and fine structural details, such as bicyclic angles, have been reproduced to within experimental accuracy. Pressure response of the structure was obtained to isostatic pressure up to 25 GPa, in increments of 1 GPa. Evolution of space group symmetry and the bicyclic angle were mapped as a function of pressure. A previously unknown phase transformation has been identified around 14 GPa of isostatic pressure. Total energies of the phases before and after phase transformation are nearly identical, with a phase transformation barrier of 0.9 eV. The study opens up the door to reliable DFT investigations of chemical reactions of crystalline aromatic systems under high pressure (e.g. formation of amorphous sp3 hybridized phases).

Type
Research Article
Copyright
Copyright © Materials Research Society 2011

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References

REFERENCES

[1] Roychowhury, P.; Basak, B. S.; Acta Cryst. (1975) B31 1559.10.1107/S0567740875005687Google Scholar
[2] Bini, R.; Proceedings of the International School of Physics “Enrico Fermi” (2002) 147 455.Google Scholar
[3] Dunitz, J. D.; Mol. Cryst. Liq. Cryst. (1996) 279 209.Google Scholar
[4] Citroni, M.; Costantiani, B.; Bini, R.; Schettino, V.; J. Phys. Chem. B (2009) 113 13526.10.1021/jp907169pGoogle Scholar
[5] Lautie, A.; Lautie, M. F.; Gruger, A.; Fahkri, S. A.; Spectrochim. Acta (1980) 36A 85.10.1016/0584-8539(80)80062-6Google Scholar
[6] Sun, H.; Mumby, S. J., Maple, J. R.; Hagler, A. T.; J. Am. Chem. Soc. (1994) 116 2978.Google Scholar
[7] Sun, H.; Macromolecules (1995) 28 701.10.1021/ma00107a006Google Scholar
[8] Clark, S. J., Segall, M. D., Pickard, C. J., Hasnip, P. J., Probert, M. J., Refson, K., Payne, M. C.. Zeitschrift fuer Kristallographie. 220(5-6) pp. 567570 (2005)Google Scholar
[9] Perdew, J.P.; Burke, K.; Ernzerhof, M.Generalized Gradient Approximation Made Simple”, Phys. Rev. Lett., 77, 38653868 (1996).10.1103/PhysRevLett.77.3865Google Scholar
[10] Tkatchenko, A. and Scheffler, M.. PRL 102, 073005 (2009)10.1103/PhysRevLett.102.073005Google Scholar