The paper is concerned with the practical determination of the characteristic values and functions of the wave equation of Schrodinger for a non-Coulomb central field, for which the potential is given as a function of the distance r from the nucleus.The method used is to integrate a modification of the equation outwards from initial conditions corresponding to a solution finite at r = 0, and inwards from initial conditions corresponding to a solution zero at r = ∞, with a trial value of the parameter (the energy) whose characteristic values are to be determined; the values of this parameter for which the two solutions fit at some convenient intermediate radius are the characteristic values required, and the solutions which so fit are the characteristic functions (§§ 2, 10).Modifications of the wave equation suitable for numerical work in different parts of the range of r are given (§§ 2, 3, 5), also exact equations for the variation of a solution with a variation in the potential or of the trial value of the energy (§ 4); the use of these variation equations in preference to a complete new integration of the equation for every trial change of field or of the energy parameter avoids a great deal of numerical work.For the range of r where the deviation from a Coulomb field is inappreciable, recurrence relations between different solutions of the wave equations which are zero at r = ∞, and correspond to terms with different values of the effective and subsidiary quantum numbers, are given and can be used to avoid carrying out the integration in each particular case (§§ 6, 7).Formulae for the calculation of first order perturbations due to the relativity variation of mass and to the spinning electron are given (§ 8).The method used for integrating the equations numerically is outlined (§ 9).

This paper is concerned with methods of evaluating numerical solutions of the non-linear partial differential equationwheresubject to the boundary conditionsA, k, q are known constants.Equation (1) is of the type which arises in problems of heat flow when there is an internal generation of heat within the medium; if the heat is due to a chemical reaction proceeding at each point at a rate depending upon the local temperature, the rate of heat generation is often defined by an equation such as (2).

The differential analyser has been used to evaluate solutions of the equationwith boundary conditions y = y′ = 0 at x = 0, y′ → 1 as x → ∞, which occurs in Falkner and Skan's approximate treatment of the laminar boundary layer. A numerical iterative method has been used to improve the accuracy of the solutions, and the results show that the accuracy of the machine solutions is about 1 in 1000, or rather better.It is shown that the conditions are insufficient to specify a unique solution for negative values of β a discussion of this situation is given, and it is shown that for the application to be made of the solution the appropriate condition is that y′ → 1 from below, and as rapidly as possible, as x → ∞. The condition that y′ → 1 from below can be satisfied only for values of β0, greater than a limiting value β0, whose value is approximately − 0·199, and which is related to the point at which the laminar boundary layer breaks away from the boundary.

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 nk 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).

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