Electron correlation in Li+, He, H− and the critical nuclear charge system ZC: energies, densities and Coulomb holes

This paper presents high accuracy correlation energies, intracule densities and Coulomb hole(s) for the lithium cation, helium, hydride ion and the system with the critical nuclear charge, Z_C, for binding two electrons. The fully-correlated (FC) wavefunction and the Hartree-Fock (HF) wavefunction are both determined using a Laguerre-based wavefunction. It is found that for the lithium cation and the helium atom a secondary Coulomb hole is present, in agreement with a previous literature finding, confirming a counter-intuitive conclusion that electron correlation can act to bring distant electrons closer together. However, no evidence for a tertiary Coulomb hole is found. For the hydride anion and the system just prior to electron detachment only a single Coulomb hole is present and electron correlation decreases the probability of finding the electrons closer together at all radial distances. The emergence of a secondary Coulomb hole is investigated and found to occur between Z = Z = 1...本论文报道了锂离子、氦原子、氢负离子以及用于束缚两个电子的临界核电荷（Z_C）体系的高精度关联能、电子对内密度与库仑空穴。本研究采用基于拉盖尔多项式的波函数，同时求解了全关联（FC）波函数与哈特利-福克（HF）波函数。研究发现，对于锂离子与氦原子体系，存在次级库仑空穴，这与此前文献报道的结果一致，验证了一个反直觉的结论：电子关联作用可使相距较远的电子彼此靠近。然而，并未发现存在三级库仑空穴的证据。对于氢负离子与即将发生电子脱离的体系，仅存在单个库仑空穴，且电子关联作用在所有径向距离下均降低了两电子近距离出现的概率。本研究对次级库仑空穴的出现条件进行了探究，发现其出现在Z=Z=1……