The current status of gaseous transport studies of the singly-charged lanthanide and actinide ions is reviewed in light of potential applications to superheavy ions. The measurements and calculations for the mobility of lanthanide ions in He and Ar agree well, and they are remarkably sensitive to the electronic configuration of the ion, namely, whether the outer electronic shells are 6s, 5d6s or 6s. The previous theoretical work is extended here to ions of the actinide family with zero electron orbital momentum: Ac (7s, S), Am (5f7s S°), Cm (5f7s S°), No (5f7s S), and Lr (5f7s S). The calculations reveal large systematic differences in the mobilities of the 7s and 7s groups of ions and other similarities with their lanthanide analogs. The correlation of ion-neutral interaction potentials and mobility variations with spatial parameters of the electron distributions in the bare ions is explored through the ionic radii concept. While the qualitative trends found for interaction potentials and mobilities render them appealing for superheavy ion research, lack of experimental data and limitations of the scalar relativistic approaches in use make further efforts necessary to bring the transport measurements into the inventory of techniques operating in "one atom at a time" mode.
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http://dx.doi.org/10.3389/fchem.2020.00438 | DOI Listing |
J Chem Phys
December 2023
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
Although it plays a critical role in the photophysics and catalysis of lanthanides, spin-orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin-orbit multiconfiguration second-order quasi-degenerate perturbation theory.
View Article and Find Full Text PDFJ Chem Phys
September 2022
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
The precise ionization energy of praseodymium oxide (PrO) seeded in supersonic molecular beams is measured with mass-analyzed threshold ionization (MATI) spectroscopy. A total of 33 spin-orbit (SO) states of PrO and 23 SO states of PrO are predicted by second-order multiconfigurational quasi-degenerate perturbation (MCQDPT2) theory. Electronic transitions from four low-energy SO levels of the neutral molecule to the ground state of the singly charged cation are identified by combining the MATI spectroscopic measurements with the MCQDPT2 calculations.
View Article and Find Full Text PDFFront Chem
May 2020
Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, Moscow, Russia.
The current status of gaseous transport studies of the singly-charged lanthanide and actinide ions is reviewed in light of potential applications to superheavy ions. The measurements and calculations for the mobility of lanthanide ions in He and Ar agree well, and they are remarkably sensitive to the electronic configuration of the ion, namely, whether the outer electronic shells are 6s, 5d6s or 6s. The previous theoretical work is extended here to ions of the actinide family with zero electron orbital momentum: Ac (7s, S), Am (5f7s S°), Cm (5f7s S°), No (5f7s S), and Lr (5f7s S).
View Article and Find Full Text PDFMolecules
April 2016
Department of Physical and Analytical Chemistry, Tomsk Polytechnic University, Tomsk 634050, Russia.
The catalytic properties of modified Au/TiO₂ catalysts for low-temperature CO oxidation are affected by deactivation and reactivation after long-term storage and by redox treatments. The effect of these phenomena on the catalysts was studied by HRTEM, BET, SEM, FTIR CO, XPS and H₂ TPR methods. The main cause for the deactivation and reactivation of catalytic properties is the variation in the electronic state of the supported gold, mainly, the proportion of singly charged ions Au⁺.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
December 2015
Department of Chemistry, Wayne State University, Detroit, MI, 48202, USA.
The analytical utility of a new and simple to use ionization method, matrix-assisted ionization (MAI), coupled with ion mobility spectrometry (IMS) and mass spectrometry (MS) is used to characterize a 2-armed europium(III)-containing poly(ethylene glycol) (Eu-PEG) complex directly from a crude sample. MAI was used with the matrix 1,2-dicyanobenzene, which affords low chemical background relative to matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). MAI provides high ion abundance of desired products in comparison to ESI and MALDI.
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