Lanthanide oxide cluster ions generated by vacuum laser ablation. Metal valence effects on cluster compositions

Journal Article · Thu Nov 03 04:00:00 EST 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100095a014· OSTI ID:7079737

Gibson, J K ^[1]

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1. Oak Ridge National Lab., TN (United States)

Pulsed XeCl excimer laser ablation ([gamma] = 308 nm; irradiance approximately 10 MW cm[sup [minus]2]) of hydrated lanthanide oxalates into vacuum has been found to generate significant yields of lanthanide oxide cluster ions, the compositions of which were analyzed by reflection time-of-flight mass spectrometry. Cluster ions, Ln[sub m]O[sup +][sub n], were identified for all of the lanthanides studied: Ln = Sm, Eu, Gd, Tb, and Yb. In each case, ions with metal contents (m) of up to at least 26 were detected, with the largest cluster identified being Tb[sub 63]O[sub 94][sup +] (mass = 11 516 amu). A distinctive sequence of cluster compositions was found for each Ln, apparently reflecting the relative accessibilities of the +2, +3, and +4 oxidation states. On the basis of the observed cluster stoichiometry distributions, it was concluded that trivalent metal sites were dominant in each series of Ln[sub m]O[sup +][sub n]. However, cluster ions were identified for Sm and Gd. A double-chain polymeric lanthanide oxide schematic structure is postulated to provide a coherent picture of the observed clustering behaviors. 40 refs., 9 figs., 4 tabs.

• DOE Contract Number: AC05-84OR21400
• OSTI ID: 7079737
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:44; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ABLATION
CARBOXYLIC ACID SALTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
DYNAMIC MASS SPECTROMETERS
EUROPIUM COMPOUNDS
EUROPIUM OXIDES
EVAPORATION
EXCIMER LASERS
GADOLINIUM COMPOUNDS
GADOLINIUM OXIDES
GAS LASERS
HALIDES
HALOGEN COMPOUNDS
HEATING
ION PAIRS
LASER-RADIATION HEATING
LASERS
MASS SPECTRA
MASS SPECTROMETERS
MEASURING INSTRUMENTS
MOLECULAR STRUCTURE
OXALATES
OXIDES
OXYGEN COMPOUNDS
PHASE TRANSFORMATIONS
PLASMA HEATING
RARE EARTH COMPOUNDS
RARE GAS COMPOUNDS
SAMARIUM COMPOUNDS
SAMARIUM OXIDES
SPECTRA
SPECTROMETERS
STOICHIOMETRY
SYNTHESIS
TERBIUM COMPOUNDS
TERBIUM OXIDES
TIME-OF-FLIGHT MASS SPECTROMETERS
TIME-OF-FLIGHT SPECTROMETERS
VACUUM EVAPORATION
VALENCE
XENON CHLORIDES
XENON COMPOUNDS
YTTERBIUM COMPOUNDS
YTTERBIUM OXIDES