• Green’s functions in quantum chemistry II. Improving the Σ perturbation approach

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    • Keywords


      Green’s functions; perturbation theory; electronic structure calculations

    • Abstract


      Two methods, which are expected to lead to results better than those of theΣ perturbation approach given earlier are investigated. Within the algebraic approximation, the methods are applied to the hydrogen molecule and to ethylene in the Pariser-Parr-Pople (PPP) approximation. Both the methods are seen to suffer from the defect of not conserving the number of particles in the system. The methods are (a) the use of a partitioning other than Hartee-Fock. Due to the non-conservation of particle number, the method does not seem to be suited for the calculation of the ground state energy, but it gives good results for ionisation potentials. The investigation reveals that the only partitioning which conserves the number of particles is the Hartree-Fock partitioning (b) the renormalisedΣ perturbation method, suggested by Csnak and others. For ethylene in the PPP approximation, the method does conserve the number of particles (but not in general). However, the energy obtained is not as good as that in theΣ perturbation method. This method therefore seems to be of limited applicability in molecular calculations.

    • Author Affiliations


      K L Sebastian1 P Narayanan1 K T Rama Varma1

      1. Department of Chemistry, Calicut University, Kerala - 673 635
    • Dates

  • Pramana – Journal of Physics | News

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