Transferability of electron pairs between H2O and H2O2

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Abstract
The transferability of strongly orthogonal geminals between H2O and H2O2 is investigated. Wavefunctions for H2O are constructed from the appropriate geminals in H2O2. Likewise, except for optimization of the oxygen‐oxygen bond geminal (ΛOO), wavefunctions for H2O2 are constructed from the appropriate geminals in H2O. The results are encouraging. In all cases, the energies of the wavefunctions constructed from the transferred geminals are actually lower than the energies of the optimum MO wavefunctions and are close to the energies of the optimum geminal wavefunctions. The optimum geminals of H2O are compared with those of H2O2. The corresponding geminals are found to be almost identical. Some factors which influence the success of geminal transferability are examined. In particular, a view of geminal localization is presented, and shielding and inductive effects are discussed. Owing to substantial shielding of the secondary oxygen nucleus in H2O2, the effective fields seen by the OH geminals turn out to be quite similar in the two molecules. The slight change in the structure of ΛOH that occurs in going from H2O to H2O2 is compatible with the slight difference in the effective field associated with ΛOH in H2O2 as compared to H2O. This effective field difference is reflected in a small kinetic energy (bond energy) change for ΛOH.