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Journal Articles Journal of Physical Chemistry A Year : 2024

Modified expression for the Hamiltonian expectation value exploiting the short-range behavior of the wave function

Abstract

The expectation value of the Hamiltonian using a model wave function is widely used to estimate the eigenvalues of electronic Hamiltonians. We explore here a modified formula for models based on long-range interaction. It scales differently the singlet and triplet component of the repulsion between electrons not present in the model (its short-range part). The scaling factors depend uniquely on the parameter used in defining the model interaction, and are constructed using only exact properties. We show results for the ground states and low-lying excited states of Harmonium with two to six electrons. We obtain important improvements for the estimation of the exact energy, not only over the model energy, but also over the expectation value of the Hamiltonian.
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Dates and versions

hal-04586442 , version 1 (24-05-2024)

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Anthony Scemama, Andreas Savin. Modified expression for the Hamiltonian expectation value exploiting the short-range behavior of the wave function. Journal of Physical Chemistry A, 2024, 128 (24), pp.4923-4935. ⟨10.1021/acs.jpca.4c01888⟩. ⟨hal-04586442⟩
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