J. Chem. Phys 144, 214905 (2016)

ISSN: 0021-9606, SCI

Density-functional description of polymer crystals: A comparative study of recent van der Waals functionals

Thinh H. Pham, Rampi Ramprasad and Huy-Viet Nguyen

Due to the lack of treatment of long-range dispersion energies, density functional theory with local and semilocal approximations of exchange-correlation energy is known to fail in describing van der Waals complexes, including polymer crystals. This limitation can be overcome by using a different class of functionals, called van der Waals density functional (vdW-DF), originally developed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. In this work, we performed a systematic study of structural properties of polymeric crystals using the original vdW-DF functional by Dion et al. and its variants and refinements. Our study shows that this class of functional outperforms the conventional LDA or PBE functionals and gives results with similar accuracy to that of empirical dispersion-corrected schemes such as DFT-D. This study suggests the use of vdW-DF2 functional — a revised version of vdW-DF functional — to obtain a high-fidelity prediction of structural and other properties of polymeric materials.

URL: http://scitation.aip.org/content/aip/journal/jcp/144/21/10.1063/1.4953170

DOI: 10.1063/1.4953170

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