• On the hierarchy equations of the wave-operator for open-shell systems

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    • Keywords


      Many-body theory; non-perturbative open-shell theory; atoms; molecules

    • Abstract


      Starting with the open-shell analogue of the Gell Mann-Low theorem of many-body perturbation theory, a non-perturbative linear operator equation is derived for the linked part of the wave-operatorW for open-shell systems. It is shown that, for a proper treatment of the linked nature of the wave-operator, a separation into its connected and disconnected components has to be made, and this leads to a hierarchy of equations for the various connected components. It is proved that the set of equations can be cast into a form equivalent to the non-perturbative equations of the wave-operator recently derived by Mukherjee and others in a coupled-cluster or exp(T) type formalism if a consistent use is made of a ‘core-valence separability’ condition introduced earlier. A comparison of the coupled-cluster representation ofW with the perturbative representation reveals that various alternative forms ofW in the coupled-cluster representation are possible and these reflect alternative ways of realising the core-valence expansion of the wave-operator. In particular it is emphasised how the use of Mandelstam block-ordering simplifies the coupled-cluster theories to a considerable extent and a comparison is made with coupled-cluster methods for open-shells put forward very recently by Ey and Lindgren. Finally, it is shown how difference energies of interest may be derived in a compact manner using the Mandelstam block-ordering of the wave-operator.

    • Author Affiliations


      Debashis Mukherjee1

      1. Department of Physical Chemistry, Indian Association for the Cultivation of Science, Calcutta - 700 032
    • Dates

  • Pramana – Journal of Physics | News

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      Posted on July 25, 2019

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