期刊
MOLECULAR PHYSICS
卷 114, 期 7-8, 页码 1086-1097出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268976.2015.1137643
关键词
DFT; Kohn-Sham potential; HOMO nodal plane; asymptotic density
资金
- Netherlands Science Foundation NWO [700.59.428]
- WCU (World Class University) program: Korea Science and Engineering Foundation [R32-2008-000-10180-0]
It is known that the asymptotic decay of the electron density outside a molecule is informative about its first ionisation potential I-0, . This dictates the orbital energy of the highest occupied Kohn-Sham (KS) molecular orbital (HOMO) to be epsilon(H) = -I-0, if the KS potential goes to zero at infinity. However, when the KS HOMO has a nodal plane, the KS density in that plane will decay as . Conflicting proposals exist for the KS potential: from exact exchange calculations it has been found that the KS potential approaches a positive constant in the plane, but from the assumption of isotropic decay of the exact (interacting) density, it has been concluded this constant needs to be negative. Here, we show that either (1) the exact density decays differently (according to the second ionisation potential I-1) in the HOMO nodal plane than elsewhere, and the KS potential has a regular asymptotic behaviour (going to zero everywhere) provided that epsilon(H - 1) = -I-1; or (2) the density does decay like everywhere but the KS potential exhibits strongly irregular if not divergent behaviour around (at) the nodal plane. [GRAPHICS] .
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据