Perturbation Theory for Atomic and Molecular Properties

  • Stephen Wilson


Perturbation theory is the most general and systematic technique for the approximate solution of quantum-mechanical eigenvalue problems. It is assumed that the eigenproblem for some model problem that affords a reasonable zero-order approximate solution to the problem of interest can be solved exactly. A perturbation, H 1, is added to the zero-order Hamiltonian, H 0, associated with the model problem, in order to recover the full Hamiltonian for the system, H. A parameter, λ, is introduced in the Hamiltonian, H= H 0 + λH 1, so as to interpolate between the zero-order Hamiltonian, λ = 0, and the full Hamiltonian, λ = 1. By making expansion in powers of λ for the exact energy and the exact wave function, and then equating the coefficients for each power of λ, a set of equations can be obtained which are then employed to obtain corrections to the zero-order energy and wave function.


Perturbation Theory Algebraic Expression Principal Term Energy Coefficient Perturbation Operator 
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Copyright information

© Springer Science+Business Media New York 1992

Authors and Affiliations

  • Stephen Wilson
    • 1
  1. 1.Rutherford Appleton LaboratoryChilton, OxfordshireEngland

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