Seniority-Zero Canonical Transformation Theory: Reducing Truncation Error with Late Truncation
arXiv:2511.07580 · doi:10.1021/acs.jctc.5c01892
Abstract
We show how to add the effects of residual electron correlation to a reference seniority-zero wavefunction by making a unitary transformation of 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 Hartree.
37 pages, 6 figures