
A new general approach is introduced for defining an optimum zero-order Hamiltonian for Rayleigh–Schrödinger perturbation theory. Instead of taking the operator directly from a model problem, it is constructed to be a best fit to the exact Hamiltonian within any desired functional form. When applied to many-body perturbation theory for electrons, strongly improved convergence is observed in cases where the conventional Fock Hamiltonian leads to divergence or slow convergence.
Chemical Physics (physics.chem-ph), Quantum Physics, Condensed Matter - Strongly Correlated Electrons, Strongly Correlated Electrons (cond-mat.str-el), Physics - Chemical Physics, FOS: Physical sciences, Quantum Physics (quant-ph)
Chemical Physics (physics.chem-ph), Quantum Physics, Condensed Matter - Strongly Correlated Electrons, Strongly Correlated Electrons (cond-mat.str-el), Physics - Chemical Physics, FOS: Physical sciences, Quantum Physics (quant-ph)
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