Simplified reference wave functions for multireference perturbation theory

David Robinson, Joseph J W McDouall

    Research output: Contribution to journalArticlepeer-review


    A number of simplifications in defining the reference wave functions used in multireference second-order Møller-Plesset perturbation theory (MRMP2) calculations are studied. The usual multiconfigurational orbital optimization is avoided by using Hartree-Fock or Kohn-Sham orbitals; the complete configuration expansion in the active-space orbitals is replaced by a severely truncated expansion, and the spin-component-scaling idea is applied to the multireference perturbation expansion. We assess these approximations to the full procedure by calculating the barrier heights for 15 processes taken from the Zhao-Gonzalez-Garcia-Truhlaø database. Our results suggest that reliable and relatively cheap reference wave functions for MRMP2 calculations can be obtained from the simplifications introduced here. We hope that this will enable the application of the MRMP2 method to a larger range of chemical systems. © 2007 American Chemical Society.
    Original languageEnglish
    Pages (from-to)9815-9822
    Number of pages7
    JournalJournal of Physical Chemistry A
    Issue number39
    Publication statusPublished - 4 Oct 2007


    • MP2 (MRMP2
    • simplified ref. wave functions for multireference MP2 theory)
    • Potential barrier (reaction barrier heights
    • Algorithm
    • Electronic wave function (simplified ref. wave functions for multireference MP2 theory)
    • ref wave function multireference MP2 MRMP2


    Dive into the research topics of 'Simplified reference wave functions for multireference perturbation theory'. Together they form a unique fingerprint.

    Cite this