Seniority-Zero Canonical Transformation Theory: Error Reduction via Late Truncation

We show how to add the effects of residual electron correlation to a reference seniority-zero wave function by transforming the true electronic Hamiltonian into seniority-zero form. The transformation is treated via the Baker–Campbell–Hausdorff (BCH) expansion, and the seniority-zero structure of the reference is exploited to evaluate the first three commutators exactly; the remaining contributions are handled with a recursive commutator approximation, as is typical in canonical transformation methods. By choosing a seniority-zero reference and using parallel computation, this method is practical for small- to medium-sized systems. Numerical tests show high accuracy, with errors ∼10 –4 Hartree.