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Updated: May 10, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Correlated one-body potential from second-order Møller-Plesset perturbation theory: alternative to orbital-optimized
Tran Nguyen Lan1, Takeshi Yanai
1The Graduate University for Advanced Studies, Myodaiji, Okazaki, Aichi 444-8585, Japan. lantran@ims.ac.jp
Abstract:
A mean-field (or one-particle) theory to represent electron correlation at the level of the second-order Møller-Plesset perturbation (MP2) theory is presented. Orbitals and associated energy levels are given as eigenfunctions and eigenvalues of the resulting one-body (or Fock-like) MP2 Hamiltonian, respectively. They are optimized in the presence of MP2-level correlation with the self-consistent field procedure and used to update the MP1 amplitudes including their denominators. Numerical performance is illustrated in molecular applications for computing reaction energies, applying Koopmans' theorem, and examining the effects of dynamic correlation on energy levels of metal complexes.
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