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r 12-Dependent terms in the wave function as closed sums of partial wave amplitudes for large l
Authors:Werner Kutzelnigg
Institution:(1) Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-4630 Bochum, Federal Republic of Germany
Abstract:The ansatz PSgr= (1+1/2r12)PHgr+chi with PHgr the bare nuclear (or screened nuclear) wave function and chi expanded in products of one-electron functions is explored for second-order perturbation theory and for variational calculations of the ground state of Helium-like ions.The energy increments E l (2) corresponding to the partial wave expansion of chi go asymptotically as l–8, while conventional partial wave increments go as l–4. chi is coupled to PHgr by a ldquoresidualrdquo interaction U12 that has no singularity for r12=0. With the present ansatz it is sufficient to include l-values up to 5 in order to get the second-order energy accurate to one microhartree. For the same accuracy lle4 is sufficient in a ldquoCI with correlated reference functionrdquo while in conventional CI one must go to lsim50. The surprisingly faster convergence of the variational approach as compared to second-order perturbation theory is explained. The slow convergence of the traditional partial wave expansion is entirely due to the attempt to represent the quantity 1=langPHgr¦r12r12 –1¦PHgrrang by its partial wave expansion. The best reference function PHgr shows very little shielding and resembles closely the eigenstate of the bare nuclear Hamiltonian. The generalization to arbitrary systems is discussed and it is pointed out that the calculation of ldquodifficultrdquo integrals can be avoided without a significant loss in accuracy.
Keywords:r 12-Dependent wave functions  Convergence of the CI-expansion  (1/Z)-Expansion  Correlation cusp  He-isoelectronic series  Hylleraas-CI
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