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Journal Article

Natural orbitals of the ground state of the two-electron harmonium atom

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Cioslowski,  Jerzy
Max Planck Institute for the Physics of Complex Systems, Max Planck Society;

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Citation

Cioslowski, J. (2018). Natural orbitals of the ground state of the two-electron harmonium atom. Theoretical Chemistry Accounts, 137(12): 173. doi:10.1007/s00214-018-2362-5.


Cite as: http://hdl.handle.net/21.11116/0000-0002-9DA5-3
Abstract
The radial components of the natural orbitals (NOs) pertaining to the 1 S + ground state of the two- electron harmonium atom are found to satisfy homogeneous differential equations at the values of the confinement strength omega omega at which the respective correlation factors are given by polynomials. Together with the angular momentum l of the NOs, the degrees of these polynomials determine the orders of the differential equations, eigenvalues of which (arising from well- defined boundary conditions) yield the natural amplitudes. In the case of l = 0, analysis of these equations uncovers certain properties of the NOs whereas application of a WKB- like approximation produces asymptotic expressions for both the NOs and the corresponding natural amplitudes that hold when the latter are small negative numbers. Extensive numerical calculations reveal that these expressions remain valid for arbitrary values of omega. The approximate s- type NOs, which are remarkably accurate at sufficiently small radial distances and exhibit universal scaling, differ qualitatively from the eigenfunctions of the core Hamiltonian even at the omega. 8 limit of vanishing electron correlation.