The generalized mean field configuration interaction method

Abstract : The mean field configuration interaction (MFCI) method is a variational approximation method that has been developed to solve the Schrödinger equation for molecular vibrations (VMFCI) and electrons (EMFCI). The Rayleigh-Schrödinger perturbation theory generalized to eigen-operators in non-commutative rings has been proposed to solve the Schrödinger equation for molecular rotation-vibration degrees of freedom. In the present work, the two approaches are merged in a unified method, the perturbative ansatz giving a ''generalized mean field'' for the MFCI approach. At order one of perturbation, the MFCI method is recovered. However, higher orders give more accurate mean fields taking better into account the coupling of the so-called ''active'' and ''spectator'' degrees of freedom (DOF) defined in a MFCI step. The new method has increased flexibility, since not only one can build any hierarchy of partitions of the system DOF as in the MFCI method, but one can also tune up the perturbation order at each MFCI step for each subset of DOF. An illustrative calculation of methane ro-vibrational spectrum is presented.
Document type :
Preprints, Working Papers, ...
Complete list of metadatas

Cited literature [1 references]  Display  Hide  Download

https://hal.univ-cotedazur.fr/hal-00785488
Contributor : Patrick Cassam-Chenaï <>
Submitted on : Wednesday, February 6, 2013 - 11:34:28 AM
Last modification on : Friday, January 12, 2018 - 1:51:43 AM
Long-term archiving on : Monday, June 17, 2013 - 7:47:52 PM

Files

Identifiers

  • HAL Id : hal-00785488, version 1

Collections

Citation

Patrick Cassam-Chenaï. The generalized mean field configuration interaction method. 2013. ⟨hal-00785488⟩

Share

Metrics

Record views

412

Files downloads

208