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Drachmanization revisited.

Jerzy Cioslowski1

  • 1Institute of Physics, University of Szczecin, Wielkopolska 15, 70-451 Szczecin, Poland and Max-Planck-Institut für Physik komplexer Systeme, Nöthnitzer Straße 38, 01187 Dresden, Germany.

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The Hiller-Sucher-Feinberg (HSF) and Drachman formalisms enhance expectation value accuracy for singular operators using approximate wavefunctions. New functionals and proven properties of densities offer improved computational methods in quantum chemistry.

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Area of Science:

  • Quantum Chemistry
  • Computational Physics

Background:

  • Accurate computation of expectation values for singular operators is crucial in quantum mechanics.
  • Approximate wavefunctions often lead to inaccuracies when evaluating these expectation values.

Purpose of the Study:

  • To elucidate the features of Hiller-Sucher-Feinberg (HSF) and Drachman formalisms.
  • To derive and present new functionals for improved accuracy in quantum mechanical calculations.

Main Methods:

  • Analysis of HSF and Drachman formalisms.
  • Derivation of a generalized one-electron density functional.
  • Presentation of equivalent functional formulations dependent on wavefunction accuracy.

Main Results:

  • A new generalized one-electron density functional is derived.
  • Drachmanized densities are proven to be normalizable and cusped, even from cuspless wavefunctions.
  • Relative advantages and limitations of HSF and Drachman formalisms are discussed.

Conclusions:

  • The HSF and Drachman formalisms offer improvements for calculating expectation values of singular operators.
  • Further research into alternative methods like "plain capping" and integral transformations is necessary.
  • The derived functionals provide a more accurate representation of electron densities.