Second order coalescence conditions of molecular wave functions.
Second order coalescence conditions of molecular wave functions.
复制标题
分子波函数的二阶聚结条件。
DOI：
10.1063/1.2945900
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
D. Tew
中科院分区：
文献类型：
--
作者：
D. Tew
加藤尖点条件给出了两个带电粒子聚结附近的分子波函数对粒子间分离的一阶依赖关系。我们推导出正确的二阶粒子间分离的条件，这涉及到在聚结点的波函数的二阶导数。对于全同粒子的聚并，我们给出了三阶修正的方程。除了一个普遍的，粒子依赖项，系统和状态依赖项出现在高阶条件下，我们解释为库仑屏蔽的效果。我们将我们的分析应用于量子化学的标准轨道方法，并讨论了Jastrow和R12型相关因子的影响。
Kato's cusp condition gives the exact first order dependence of molecular wave functions on interparticle separation near the coalescence of two charged particles. We derive conditions correct to second order in interparticle separation, which concern second order derivatives of the wave function at the coalescence point. For identical particle coalescence, we give equations correct to third order. In addition to a universal, particle dependent term, a system and state dependent term arises in the higher order conditions, which we interpret as an effect of Coulombic screening. We apply our analysis to the standard orbital-based methods of quantum chemistry and discuss the implications for Jastrow- and R12-type correlation factors.