BEHAVIOR OF ELECTRONIC WAVE FUNCTIONS NEAR CUSPS
BEHAVIOR OF ELECTRONIC WAVE FUNCTIONS NEAR CUSPS
复制标题
尖点附近电子波函数的行为
DOI：
10.1063/1.471719
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发表时间：
1996
影响因子：
4.4
通讯作者：
D. Chipman
中科院分区：
文献类型：
--
作者：
V. Rassolov;D. Chipman
众所周知，当一个电子接近原子核或另一个电子时，非相对论性多电子波函数的行为受到尖点条件的控制。这是势中库仑奇点的结果，并提供了波函数及其在聚结点的一阶导数之间的特定关系。这里表明，聚结行为还唯一地决定了球平均波函数的低阶导数的三阶导数。新关系对于任何光滑外场中的任何原子、分子或电子气都有效。还讨论了电子气系统中的电子-电子聚结和多构型自洽场波函数中的电子-核聚结的进一步扩展。
The behavior of a nonrelativistic many‐electron wave function when one electron approaches either a nucleus or another electron is well known to be governed by a cusp condition. This is a consequence of the Coulomb singularity in the potential and provides a specific relation between the wave function and its first derivative at the point of coalescence. It is shown here that the coalescence behavior also uniquely determines the third derivative of the spherically averaged wave function in terms of the lower derivatives. The new relation is valid for any atom, molecule, or electron gas in any smooth external field. Further extensions are also discussed for electron–electron coalescence in electron gas systems and for electron–nucleus coalescence in multiconfigurational self‐consistent‐field wave functions.