Approximate natural orbitals via the biorthogonal valence bond method

Abstract
A method is introduced for determining an initial approximation to the first‐order density matrix and natural orbitals of a molecular system within the valence bond formalism. The nonorthogonality problem usually associated with these calculations is avoided by using a dual biorthogonal basis set. Results of test calculations are presented and the feasibility of using this method in large‐scale natural orbital CI calculations is discussed.

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