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

Journal Article · Thu Nov 03 00:00:00 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), Vol. 98:44; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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