期刊
MOLECULAR PHYSICS
卷 111, 期 14-15, 页码 2147-2153出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268976.2013.793834
关键词
vibrational spectroscopy; atom centered potentials; plane-wave and pseudopotentials; high-performance computing
资金
- Office of Science of the U.S. DOE [DE-AC02-06CH11357]
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 H-2, F-2, Cl-2 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.
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