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Force correcting atom centered potentials for generalized gradient approximated density functional theory : approaching hybrid functional accuracy for geometries and harmonic frequencies in small chlorofluorocarbons

von Lilienfeld, O. Anatole. (2013) Force correcting atom centered potentials for generalized gradient approximated density functional theory : approaching hybrid functional accuracy for geometries and harmonic frequencies in small chlorofluorocarbons. Molecular Physics, 111 (14-15). pp. 2147-2153.

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Official URL: http://edoc.unibas.ch/dok/A6223603

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Abstract

Generalised gradient approximated (GGA) density functional theory (DFT) typically overestimates polarisability and bond-lengths, and underestimates force constants of covalent bonds. To overcome this problem we show that one can use empirical force correcting atom centred potentials (FCACPs), parametrised for every nuclear species. Parameters are obtained through minimisation of a penalty functional that explicitly encodes hybrid DFT forces and static polarisabilities of reference molecules. For hydrogen, fluorine, chlorine and carbon the respective reference molecules consist of H2, F2, Cl2 and CH4. The transferability of this approach is assessed for harmonic frequencies in a small set of chlorofluorocarbon molecules. Numerical evidence, gathered for CF4, CCl4, CCl3F, CCl2F2, CClF3, ClF, HF, HCl, CFH3, CF2H2, CF3H, CHCl3, CH2Cl2 and CH3Cl indicates that the GGA+FCACP level of theory yields harmonic frequencies that are significantly more consistent with hybrid DFT values, as well as slightly reduced molecular polarisability.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Taylor & Francis
ISSN:0026-8976
e-ISSN:1362-3028
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:12 Apr 2017 12:02
Deposited On:27 Mar 2014 13:12

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