Parametrization of free ion levels of four isoelectronic 4f² systems: Insights into configuration interaction parameters

Yau Yuen YEUNG, Peter Anthony TANNER

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13 Citations (Scopus)

Abstract

The experimental free ion 4f² energy level data sets comprising 12 or 13 J-multiplets of La⁺, Ce²⁺, Pr³⁺ and Nd⁴⁺ have been fitted by a semiempirical atomic Hamiltonian comprising 8, 10, or 12 freely-varying parameters. The root mean square errors were 16.1, 1.3, 0.3 and 0.3 cm⁻¹, respectively for fits with 10 parameters. The fitted inter-electronic repulsion and magnetic parameters vary linearly with ionic charge, i, but better linear fits are obtained with (4−i)², although the reason is unclear at present. The two-body configuration interaction parameters α and β exhibit a linear relation with [ΔE(bc)]⁻¹, where ΔE(bc) is the energy difference between the 4f² barycentre and that of the interacting configuration, namely 4f6p for La⁺, Ce²⁺, and Pr³⁺, and 5p⁵4f³ for Nd⁴⁺. The linear fit provides the rationale for the negative value of α for the case of La⁺, where the interacting configuration is located below 4f². Copyright © 2013 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)46-51
JournalChemical Physics Letters
Volume590
DOIs
Publication statusPublished - Dec 2013

Citation

Yeung, Y. Y., & Tanner, P. A. (2013). Parametrization of free ion levels of four isoelectronic 4f² systems: Insights into configuration interaction parameters. Chemical Physics Letters, 590, 46-51.

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