Hydration of gas-phase ytterbium ion complexes studied by experiment and theory [electronic resource].
- Published
- Berkeley, Calif. : Lawrence Berkeley National Laboratory, 2011.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy. - Physical Description
- 575 : digital, PDF file
- Additional Creators
- Lawrence Berkeley National Laboratory and United States. Department of Energy. Office of Scientific and Technical Information
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- Restrictions on Access
- Free-to-read Unrestricted online access
- Summary
- Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX₂⁺ and YbX(OH)⁺ (X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations - kinetics and extent of hydration - are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.
- Report Numbers
- E 1.99:lbnl-4353e
lbnl-4353e - Subject(s)
- Other Subject(s)
- Note
- Published through SciTech Connect.
02/11/2011.
"lbnl-4353e"
Theoretical Chemistry Accounts: Theory, Computation, and Modeling 129 3-5 ISSN 1432-881X FT
Marcalo, Joaquim; Rutkowski, Philip X; Michelini, Maria C.; Bray, Travis H.; Russo, Nino; Gibson, John K.
Chemical Sciences Division - Funding Information
- DE-AC02-05CH11231
View MARC record | catkey: 13805027