Concepedia

The Wave Mechanics of an Atom with a Non-Coulomb Central Field. Part II. Some Results and Discussion

D. R. Hartree

Mathematical Proceedings of the Cambridge Philosophical Society · 1928 · 542 citations · 3 references

Concepts

TL;DR

The study discusses the wave‑mechanical analogue of an orbital model where internal and external orbits share the same energy. The paper aims to determine a self‑consistent field for each atom that reproduces the charge distribution of its core electrons. The authors solve the central‑field wave equation for various atoms, using successive approximation to obtain a self‑consistent field and comparing the resulting charge distributions with those from other computational methods. Self‑consistent field approximations for He, Rb⁺, Na⁺, and Cl⁻ yield ionization potentials and X‑ray/optical terms that agree well with experimental values.

Abstract

The methods of solution of the wave equation for a central field given in the previous paper are applied to various atoms. For the core electrons, the details of the interaction of the electrons in a single n k group are neglected, but an approximate correction is made for the fact that the distributed charge of an electron does not contribute to the field acting on itself (§2). For a given atom the object of the work is to find a field such that the solutions of the wave equation for the core electrons in this field (corrected as just mentioned for each core electron) give a distribution of charge which reproduces the field. This is called the self-consistent field, and the process of finding it is one of successive approximation (§ 3). Approximations to the self-consistent field have been found for He (§ 4), Rb + (§ 5), Na + , Cl − (§ 9). For He the energy parameter for the solution of the wave equation for one electron in the self-consistent field of the nucleus and the other corresponds to an ionisation potential of 24·85 volts (observed 24·6 volts); this agreement suggests that for other atoms the values of the energy parameter in the self-consistent field (corrected for each core electron) will probably give good approximations to the X-ray terms (§4). The most extensive work has been carried out for Rb + . The distribution of charge given by the wave functions in the self-consistent field is compared with the distribution calculated by other methods (§ 6). The values of X-ray and optical terms calculated from the self-consistent field show satisfactory agreement with those observed (§ 7). The wave mechanical analogue of the case in which on the orbital model an internal and an external orbit of the same energy are possible is discussed (§ 8).

References

3

The calculation of atomic fields

Lippert Thomas · Mathematical Proceedings of the Cambridge Philosophical Society · 1927

+12

2.4K citations

The theoretical prediction of the physical properties of many electron atoms and ions. Mole refraction, diamagnetic susceptibility, and extension in space

Linus Pauling · Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character · 1927

527 citations

33 citations