Negative electron affinities from conventional electronic structure methods
Negative electron affinities from
conventional electronic structure methods
复制标题
传统电子结构方法的负电子亲和力
DOI：
10.1007/s00214-014-1445-1
复制
发表时间：
2014
影响因子：
1.7
通讯作者：
J. Simons
中科院分区：
文献类型：
--
作者：
K. Jordan;Vamsee K. Voora;J. Simons
摘要如果描述相互作用的势V
过量电子和基态中性或阴离子母体之间的关系是
在短程内具有足够的吸引力，电子附着态具有正值
可能会出现电子亲和势（EA）。即使潜力不够吸引人
为了产生束缚态，亚稳态电子附着态仍然可能发生并且
具有足够长的寿命以产生可通过实验检测到的特征。
当 V 的吸引分量与长程排斥贡献相结合时，就会出现低能亚稳态。
产生一个势垒，多余的电子可以暂时被捕获在该势垒后面。这些
排斥贡献来自于过量的离心势
电子的角动能或长程库仑斥力
阴离子母体。当没有势垒时，这种低能亚稳态
不会出现，但不正确的理论计算可能会导致错误
对它们存在的预测。传统的电子结构方法，在
描述了大多数微小的修改，以正确表征亚稳态
状态并避免错误地预测亚稳态的存在
具有不存在障碍的负 EA。
AbstractIf the potential V describing the interaction
between an excess electron and a ground-state neutral or anionic parent is
sufficiently attractive at short range, electron-attached states having positive
electron affinities (EAs) can arise. Even if the potential is not attractive enough
to produce a bound state, metastable electron-attached states may still occur and
have lifetimes long enough to give rise to experimentally detectable signatures.
Low-energy metastable states arise when the attractive components of V combine with a longer-range repulsive contribution to
produce a barrier behind which the excess electron can be temporarily trapped. These
repulsive contributions arise from either the centrifugal potential in the excess
electron’s angular kinetic energy or long-range Coulomb repulsion in the case of an
anionic parent. When there is no barrier, this kind of low-energy metastable state
does not arise, but improper theoretical calculations can lead to erroneous
predictions of their existence. Conventional electronic structure methods with, at
most, minor modifications are described for properly characterizing metastable
states and for avoiding incorrectly predicting the existence of metastable states
with negative EAs where no barrier is present.