Infrared spectroscopy of discrete uranyl anion complexes

Idaho National Laboratory, Idaho Falls, Idaho, USA.
The Journal of Physical Chemistry A (Impact Factor: 2.78). 02/2008; 112(3):508-21. DOI: 10.1021/jp077309q
Source: PubMed

ABSTRACT The Free-Electron Laser for Infrared Experiments (FELIX) was used to study the wavelength-resolved multiple photon photodissociation of discrete, gas-phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands and are comparable to solution-phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm(-1) higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.

  • [Show abstract] [Hide abstract]
    ABSTRACT: Electrospray ionization (ESI) in the negative ion mode was used to generate anionic, gas-phase oxo-molybdenum (MoO2+) complexes with dithiolene ligands. By varying ESI and ion transfer conditions, both doubly and singly charged forms of the complex, with identical formula, were generated. Collision-induced dissociation (CID) of the dianion generated exclusively the monoanion, while fragmentation of the monoanion involved decomposition of the dithiolene ligands. The intrinsic structure of the monoanion and the dianion were determined by using wavelength-selective infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The IRMPD spectrum for the dianionic complex exhibits absorptions that can be assigned to (ligand) C=C, C-S and C-C≡N and Mo=O stretches. Comparison of the IRMPD spectrum to spectra predicted for various possible conformations allows assignment of a pseudo square pyramidal structure with C2v symmetry, equatorial coordination of MoO2+ by the S atoms of the dithiolene ligands and a singlet spin state. A single absorption was observed for the oxidized complex. When the same scaling factor employed for the dianion is used for the oxidized version, theoretical spectra suggest that the absorption is the Mo=O stretch for a distorted square pyramidal structure and doublet spin state. A predicted change in conformation upon oxidation of the dianion is consistent with a proposed bonding scheme for the bent-metallocene dithiolene compounds [Lauher, J. W.; Hoffmann, R., J. Am. Chem. Soc. 1976, 98, 1729-42] where a large folding of the dithiolene moiety along the S...S vector is dependent on the occupancy of the in-plane metal d-orbital.
    The Journal of Physical Chemistry A 07/2014; 118(29). DOI:10.1021/jp503222v · 2.78 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Hydroxynicotinic acids (2-, 4-, 5- and 6-hydroxy) are widely used in the manufacture of industrial products, and hydroxypyridines are important model systems for study of the tautomerization of N-heterocyclic compounds. Here we determined the gas-phase structure of deprotonated 6-hydroxynicotinic acid (6OHNic). Anions were generated by electrospray ionization, and isolated and stored in a Fourier transform ion cyclotron resonance mass spectrometer. Infrared (action) spectra were collected by monitoring photodissociation yield versus photon energy. Experimental spectra were then compared with those predicted by density functional theory (DFT) and second-order Møller-Plesset (MP2) perturbation theory calculations. For neutral 6OHNic, DFT and MP2 calculations strongly suggest that the 6-pyridone tautomer is favored when solvent effects are included. The lowest energy isomer of deprotonated 6OHNic, in the aqueous or gas phase, is predicted to be the 6-pyridone structure deprotonated by the carboxylic acid group. The deprotonated, 6-pyridone structure is confirmed by comparison of the infrared multiple-photon photodissociation (IRMPD) spectrum in the region of 1100-1900 cm(-1) with those predicted using DFT and MP2 calculations. Copyright © 2014 John Wiley & Sons, Ltd.
    Rapid Communications in Mass Spectrometry 04/2014; 28(7):691-8. DOI:10.1002/rcm.6829 · 2.64 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The realistic InSb nanostructures namely InSb nanoring, InSb nanocube, InSb nanocube-18, InSb nanosheet, InSb nanocage and InSb nanocube-27 are simulated and optimized successfully using B3LYP/LanL2DZ basis set. The stability of InSb nanostructures is studied in terms of binding energy, vibrational studies and calculated energy. The electronic properties of InSb nanostructures are discussed using ionization potential, electron affinity and HOMO–LUMO gap. Point symmetry and dipole moment of InSb nanostructures are reported. Incorporation of impurity atom in InSb nanostructures is studied using embedding energy. The present study provides the information regarding the enhanced electronic properties of InSb nanostructure which finds its potential importance in microelectronics and optoelectronic devices.
    AEJ - Alexandria Engineering Journal 06/2014; DOI:10.1016/j.aej.2014.03.008

Full-text (2 Sources)

Available from
May 29, 2014