Communication: Analytic gradients in the random-phase approximation.

نویسندگان

  • Johannes Rekkedal
  • Sonia Coriani
  • Maria Francesca Iozzi
  • Andrew M Teale
  • Trygve Helgaker
  • Thomas Bondo Pedersen
چکیده

The relationship between the random-phase-approximation (RPA) correlation energy and the continuous algebraic Riccati equation is examined and the importance of a stabilizing solution is emphasized. The criterion to distinguish this from non-stabilizing solutions can be used to ensure that physical, smooth potential energy surfaces are obtained. An implementation of analytic RPA molecular gradients is presented using the Lagrangian technique. Illustrative calculations indicate that RPA with Hartree-Fock reference orbitals delivers an accuracy similar to that of second-order Mo̸ller-Plesset perturbation theory.

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عنوان ژورنال:
  • The Journal of chemical physics

دوره 139 8  شماره 

صفحات  -

تاریخ انتشار 2013