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The S-matrix Kohn variational procedure

The S-matrix version of the Kohn variational procedure is examined. It is shown that the method is a particular case of other Kohn variational procedures which have the limitation that they give results that are dependent on the asymptotic form chosen for the wavefunction. In particular it is shown that when using S-matrix boundary conditions the calculated S-matrix need not be unitary. However, if the trial functions are adapted according to the prescription previously given by Rudge (1973-80), then the calculated S-matrix is unitary and coincides with the S-matrix calculated by any of the other Kohn methods using these same basis functions. A numerical illustration is given.