Reanalysis of the Aqueous Spectrum of the Neptunyl(V) [NpO2+] Ion

Edelstein, Norman M.

doi:10.1021/acs.jpca.5b08576

Reanalysis of the Aqueous Spectrum of the Neptunyl(V) [NpO₂⁺] Ion

Journal Article · Tue Oct 20 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b08576· OSTI ID:1378643

Edelstein, Norman M. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The actinyl ions, consisting of the dioxoactinde(VI) and dioxoactinide(V) ions, are unique in the periodic table. However, very few quantitative studies of the spectra of these ions have been performed. In this paper the analysis of the optical spectrum of the aqueous neptunyl(V) [NpO₂⁺] ion in 1 M HClO₄ is reexamined. The species in solution is assumed to be the linear NpO₂⁺ ion surrounded in the equatorial plane by five oxygen atoms from five H₂O molecules. The neptunyl(V) ion has the 5f² open-shell configuration, and the low-lying optical transitions (up to 20 000 cm^-1) observed are primarily from the two 5f electrons occupying the 5f and 5fφ orbitals. The conventional parametric theory used for f n systems is applied to these low-lying transitions utilizing the intensity calculations that Matiska et al.1 have performed for this ion and the data reported by Eisenstein and Pryce.2 Possible ratios for the Slater electrostatic repulsion parameters are obtained from the data for the isoelectronic ion U⁴⁺ (5f²) in various host crystals. The results are consistent with previous crystal field analyses of the 5f 1 neptunyl(VI) [NpO₂⁺] ion.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1378643

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 45 Vol. 119; ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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