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Properties of ThFx from Infrared Spectra in Solid Argon and Neon with Supporting Electronic Structure and Thermochemical Calculations

Kanchana Thanthiriwatte, Xuefeng Wang, Lester Andrews, David Dixon, Jens Metzger, Thomas Vent-Schmidt, Sebastian Riedel – 2014

Laser-ablated Th atoms react with F₂ in condensing noble gases to give ThF₄ as the major product. Weaker higher frequency infrared absorptions at 567.2, 564.8 (576.1, 573.8) cm⁻¹, 575.1 (582.7) cm⁻¹ and 531.0, (537.4) cm⁻¹ in solid argon (neon) are assigned to the ThF, ThF₂ and ThF₃ molecules based on annealing and photolysis behavior and agreement with CCSD(T)/aug-cc-pVTZ vibrational frequency calculations. Bands at 528.4 cm⁻¹ and 460 cm⁻¹ with higher fluorine concentrations are assigned to the penta-coordinated species (ThF₃)(F₂) and ThF₅⁻. These bands shift to 544.2 and 464 cm⁻¹ in solid neon. The ThF₅ molecule has the (ThF₃)(F₂) Cs structure and is essentially the unique [ThF₃⁺][F₂⁻] ion pair based on charge and spin density calculations. Electron capture by (ThF₃)(F₂) forms the trigonal bipyramidal ThF₅⁻anion in a highly exothermic process. Extensive structure and frequency calculations were also done for thorium oxyfluorides and Th₂F₄,₆,₈ dimer species. The calculations provide the ionization potentials, electron affinities, fluoride affinities, Th–F bond dissociation energies, and the energies to bind F₂ and F₂⁻ to a cluster as well as dimerization energies.

Titel
Properties of ThFx from Infrared Spectra in Solid Argon and Neon with Supporting Electronic Structure and Thermochemical Calculations
Verfasser
Kanchana Thanthiriwatte, Xuefeng Wang, Lester Andrews, David Dixon, Jens Metzger, Thomas Vent-Schmidt, Sebastian Riedel
Datum
2014
Quelle/n
Erschienen in
J. Phys. Chem., 2014, 118, 2107-2119.
Zitierweise
DOI: 10.1021/jp412818r
Sprache
eng
Art
Text