范德华力的密度泛函在水六聚体基准集中考虑了氢键。

Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers.

作者信息

Kelkkanen André K, Lundqvist Bengt I, Nørskov Jens K

出版信息

J Chem Phys. 2009 Jul 28;131(4):046102. doi: 10.1063/1.3193462.

DOI:10.1063/1.3193462

PMID:19655929

Abstract

A recent extensive study has investigated how various exchange-correlation (XC) functionals treat hydrogen bonds in water hexamers and has shown traditional generalized gradient approximation and hybrid functionals used in density-functional (DF) theory to give the wrong dissociation-energy trend of low-lying isomers and van der Waals (vdW) dispersion forces to give key contributions to the dissociation energy. The question raised whether functionals that incorporate vdW forces implicitly into the XC functional predict the correct lowest-energy structure for the water hexamer and yield accurate total dissociation energy is here answered affirmatively for the vdW-DF [M. Dion et al., Phys. Rev. Lett.92, 246401 (2004)].

摘要

最近一项广泛的研究调查了各种交换关联（XC）泛函如何处理水六聚体中的氢键，并表明密度泛函（DF）理论中使用的传统广义梯度近似和杂化泛函给出了低能异构体错误的解离能趋势，而范德华（vdW）色散力对解离能有关键贡献。对于vdW-DF [M. Dion等人，《物理评论快报》92, 246401 (2004)]，这里对将vdW力隐含纳入XC泛函的泛函是否能预测水六聚体正确的最低能量结构并产生准确的总解离能这一问题给出了肯定的回答。