A spin-complete version of the spin-flip approach to bond breaking: What is the impact of obtaining spin eigenfunctions?

J. S. Sears, C. D. Sherrill, and A. I. Krylov
J. Chem. Phys. 118, 9084 – 9094 (2003)

Spin-complete versions of the spin-flip configuration-interaction-singles (SF-CIS) approach have been investigated to determine the impact of making the wavefunction an eigenfunction of S2. The method has been implemented within an extended restricted active space configuration interaction formalism. Spin-complete results are presented for excitation energies, equilibrium geometries, and potential energy curves for dissociation of a single bond in several small molecules. The effect of different orbital choices has also been investigated. The spin-complete results are compared both to results using the original spin-flip method and to more computationally expensive benchmarks. Using spin eigenfunctions dramatically improves upon the accuracy of the SF-CIS approach, while preserving the size-consistency of the model.

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