Theoretical Chemistry Accounts

, Volume 97, Issue 1, pp 331-340

First online:

RI-MP2: first derivatives and global consistency

  • Florian WeigendAffiliated withInstitut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany
  • , Marco HäserAffiliated withInstitut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany

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The evaluation of RI-MP2 first derivatives with respect to nuclear coordinates or with respect to an external electric field is described. The prefix RI indicates the use of an approximate resolution of identity in the Hilbert space of interacting charge distributions (Coulomb metric), i.e., the use of an auxiliary basis set to approximate charge distributions. The RI technique is applied to first derivatives of the MP2 correlation energy expression while the (restricted) Hartree-Fock reference is treated in the usual way. Computational savings by a factor of 10 over conventional approaches are demonstrated in an application to porphyrin. It is shown that the RI approximation to MP2 derivatives does not entail any significant loss in accuracy. Finally, the relative energetic stabilities of a representative sample of closed-shell molecules built from first and second row elements have been investigated by the RI-MP2 approach, and thus it is tested whether such properties that refer to potential energy hypersurfaces in a more global way can be described with similar consistency to the more locally defined derivatives.

Key words: Gradients Perturbation theory of electronic structure MP2 Electron correlation Coulomb interaction