Computation of derivatives for parameter optimization in least‐squares fitting of linear combinations of Slater‐type orbitals by Gaussians

The approximation of a linear combination of Slater‐type orbitals in terms of Gaussian functions is a many‐parameter optimization problem. Formulas for computation of the gradient of the overlap in parameter space are reported. An alternative method of computing the gradient is described, which is of general applicability. This technique permits the exact evaluation of a derivative, without derivation and programming of its analytic expression.