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

Published online by Cambridge University Press:  21 March 2011

Bohdan Schatschneider  and
Jian-jie Liang
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 wereinvestigated for crystalline indole through dispersion-corrected densityfunctional theory (DFT-D) method. An accurate, nonempirical method (as inthe latest implementations of CASTEP) is used to correct for the general DFTscheme to include van der Waals interactions important in molecularcrystals. Ambient structural details, including space group symmetry,density, and fine structural details, such as bicyclic angles, have beenreproduced to within experimental accuracy. Pressure response of thestructure was obtained to isostatic pressure up to 25 GPa, in increments of1 GPa. Evolution of space group symmetry and the bicyclic angle were mappedas a function of pressure. A previously unknown phase transformation hasbeen identified around 14 GPa of isostatic pressure. Total energies of thephases before and after phase transformation are nearly identical, with aphase transformation barrier of 0.9 eV. The study opens up the door toreliable DFT investigations of chemical reactions of crystalline aromaticsystems under high pressure (e.g. formation of amorphous sp3hybridized phases).

Keywords

biomaterialcrystallinesimulation

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References

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