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Published in

American Institute of Physics, The Journal of Chemical Physics, 8(122), p. 084102

DOI: 10.1063/1.1846655

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Collective natural orbital occupancies of harmonium

Journal article published in 2005 by Jerzy Cioslowski, Marcin Buchowiecki
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

In the harmonium atom, the collective occupancies {n(l)} of natural orbitals with different angular momenta l can be rigorously studied for those values of the confinement strength omega that lead to ground-state wave functions with correlation factors given by polynomials of kth order. Analysis of two such cases, with omega equal to 12 (k=1) and 110 (k=2), uncovers some interesting properties of {n(l)}, which turn out to be given by rational functions of pi(12) with simple coefficients. In particular, contrary to naive expectations, the collective occupancies for l>2 actually decrease upon strengthening of correlation. The explicit formulas for l-matrices and {n(l)} can be readily utilized in testing, calibration, and benchmarking of approximate implementations of the density matrix functional theory (DMFT).