Explicit Green operators for quantum mechanical Hamiltonians. I: The hydrogen atom

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Abstract: We study a new approach to determine the asymptotic behaviour of quantum many-particle systems near coalescence points of particles which interact via singular Coulomb potentials. This problem is of fundamental interest in electronic structure theory in order to establish accurate and efficient models for numerical simulations. Within our approach, coalescence points of particles are treated as embedded geometric singularities in the configuration space of electrons. Based on a general singular pseudo-differential calculus, we provide a recursive scheme for the calculation of the parametrix and corresponding Green operator of a nonrelativistic Hamiltonian. In our singular calculus, the Green operator encodes all the asymptotic information of the eigenfunctions. Explicit calculations and an asymptotic representation for the Green operator of the hydrogen atom and isoelectronic ions are presented.


The authors propose a new approach to determine the asymptotic behaviour of the eigenfunctions of nonrelativistic quantum Hamiltonians near singular points of the potential. In this paper they consider the hydrogen atom and isoelectronic ions. This Hamiltonian can be considered as a Fuchs type differential operator acting on \(\mathbb R_+\times S^2\). Therefore one can use the pseudo-differential calculus on manifolds with singularities previously developed [\textit{Y. V. Egorov} and \textit{B.-W. Schulze}, Operator Theory: Advances and Applications. 93. Basel: Birkhäuser (1997; Zbl 0877.35141)] to provide a recursive scheme for the calculation of the Green operator. The asymptotic behaviour of the eigenfunctions belonging to a fixed eigenvalue is completely characterized by the behaviour of the corresponding Green operator.




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