Intracule densities and electron correlation in the hydrogen molecule
R J Boyd; C Sarasola; J M Ugalde; R J Boyd; Kimika Fakultatea, Euskal Herriko Unibertsitatea, Euskadi, Spain; C Sarasola; Kimika Fakultatea, Euskal Herriko Unibertsitatea, Euskadi, Spain; J M Ugalde; Kimika Fakultatea, Euskal Herriko Unibertsitatea, Euskadi, Spain
Журнал:
Journal of Physics B: Atomic, Molecular and Optical Physics
Дата:
1988-07-28
Аннотация:
The spherically averaged intracule density I(r) is calculated with minimal and split-valence basis sets in the ground state of the hydrogen molecule. Restricted Hartree-Fock calculations indicate a high probability of interelectronic distances (r) of the order of 1 au as the internuclear separation (R) goes to infinity due to the incorrect dissociation of H<sub>2</sub>. The inadequacy of the restricted Hartree-Fock I(r) at large R is further illustrated by calculating (1/r) as a function of R. Configuration interaction calculations are shown to yield the correct qualitative form for I(r) at large R and when combined with the Hartree-Fock results yield the approximate Coulomb hole in H<sub>2</sub> as a function of internuclear separation. Explicit formulae for the evaluation of I(r) and its moments with s-type Gaussian basis functions are included.
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