Nonorthogonality corrections in the method of correlated basis functions

A set of normalized linearly independent basis functions φ₁, φ₂, …, φ_j, … generates matrix representatives $\text{H}$ and $\text{N}$ of the Hamiltonian operator and the identity. An orthonormal basis $\text{φ}{}_1$, $\text{φ}{}_2$, …, $\text{φ}{}_{\mathrm{j}}$, … generated by a Löwdin transformation is characterized by the distance in Hilbert space between $\text{φ}{}_{\mathrm{j}}$ and φ_j. The choice of positive definite $\text{N}$${}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ minimizes these distances and maximizes the diagonal elements of $\text{N}$${}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. Again for positive definite $\text{N}$${}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and a finite basis, 1 ? j ? p, the analysis yields a general theorem on Trace $\text{N}$${}^{\mathrm{<mtext>?n</mtext><mtext>2</mtext>}}$ (? p for all positive and negative integral values of n except n = ?1 and ? p for n = ?1).Sufficient conditions are determined which permit the application of the binomial theorem to the evaluation of the transform of $\text{H}$. Approximate formulas for the energy eigenvalues through third order in nondiagonal matrix elements are presented in a compact form containing characteristic nonorthogonality corrections depending on the exterior or interior location of the matrix element in the perturbation formulas.