Vibrational spectra (matrix and vapour phase) and molecular force field of OVCl3

Filgueira, R. R.; Fournier, L. L.; Varetti, E.L.

doi:10.1016/0584-8539(82)80046-9

Cited by 29 publications

(18 citation statements)

References 22 publications

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“…Blank experiments of each reagent in solid argon were conducted for each of the reagents in this study, prior to any co-deposition experiments. The spectra obtained in these blanks were in good agreement with literature spectra; , traces of HCl (0.01−0.05 absorbance units) were noted in all Ar/OVCl 3 experiments, and some CD 3 OH was noted in the CD 3 OD blank experiments.. These blank experiments were then annealed to approximately 35 K and recooled to 14 K and additional spectra recorded.…”

Section: Resultssupporting

confidence: 84%

Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Ault

1999

J. Phys. Chem. A

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The matrix isolation technique has been employed to investigate the reaction of OVCl3 with CH3OH. Using twin jet deposition, the initial intermediate in the mechanism was identified as a weakly bound molecular complex. This species is characterized by perturbations to the C−O, VO, and V−Cl stretching modes. Merged jet deposition, with a room-temperature reaction zone, led to complete conversion to Cl2V(O)OCH3, the second intermediate in the reaction sequence, through HCl elimination from the initial complex. This species was identified by use of extensive isotopic labeling, the observation of HCl as an additional reaction product, and by comparison to density functional calculations. All of the fundamental vibrational modes of this species that lie above 400 cm-1 were observed, some with very high intensities. Heating the reaction zone above 150 °C led to destruction of this intermediate, and production of both CH2O and CH3Cl.

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Section: Resultssupporting

confidence: 84%

Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Ault

1999

J. Phys. Chem. A

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“…Prior to any co-deposition experiments, blank experiments were run on each of the reagents used in this study, in both argon and nitrogen matrices (with the exception of ND 3 , which was studied only in nitrogen matrices). In each case, the blanks were in good agreement with literature spectra, [19][20][21][22][23] and with blanks run previously in this laboratory. The actual 15 N/ 14 N ratio in the 15 NH 3 blank, as determined by relative parent band intensities, was approximately 8/1, whereas in the ND 3 experiments, the D/H ratio was approximately 7/1, after extensive conditioning.…”

Section: Methodssupporting

confidence: 83%

“…In each case, the blanks were in good agreement with literature spectra, [19][20][21][22][23] and with blanks run previously in this laboratory. The actual 15 N/ 14 N ratio in the 15 NH 3 blank, as determined by relative parent band intensities, was approximately 8/1, whereas in the ND 3 experiments, the D/H ratio was approximately 7/1, after extensive conditioning.…”

Section: Resultsmentioning

confidence: 71%

Matrix Isolation Study of the Thermal and Photochemical Reaction of OVCl₃ with NH₃: Spectroscopic and Theoretical Characterization of Cl₂V(O)NH₂

Ault

2001

J. Phys. Chem. A

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Initial and secondary intermediates in the reaction of OVCl 3 with NH 3 have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet co-deposition of these two reagents led to a series of infrared absorptions that are assigned to the 1:1 molecular complex between these two species. Irradiation of these matrices with light of λ > 300 nm led to complete destruction of the complex, and the growth of a number of new bands. These are assigned to the Cl 2 V(O)NH 2 species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by extensive isotopic labeling ( 15 N and 2 H), as well as by B3LYP/6-311G+(2d,3p) density functional calculations. Good agreement was observed between the experimental and the computed frequencies. Similar experiments with (CH 3 ) 3 N led, at best, to a very small degree of complex formation.

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“…The calculated frequencies of VOCl 3 and OsO 4 are compared with the gas phase IR bands 36,37 in Tables VII and VIII. The low energy bending modes are typically within 10-30 cm Ϫ1 of the observed bands, even including the V-Cl stretching frequency in VOCl 3 calculated at 499 cm Ϫ1 ͑508 cm Ϫ1 expt͒.…”

Section: Vocl 3 and Osomentioning

confidence: 99%

Vibrational frequencies of transition metal chloride and oxo compounds using effective core potential analytic second derivatives

Russo

Martin

Hay

et al. 1995

The Journal of Chemical Physics

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Articles you may be interested inPerturbative treatment of scalar-relativistic effects in coupled-cluster calculations of equilibrium geometries and harmonic vibrational frequencies using analytic second-derivative techniques Shift in low-frequency vibrational spectra of transition-metal zirconium compounds Influence of an external uniform electric field on harmonic vibrational frequencies. Analytic energy second derivatives for closedshell restricted Hartree-Fock wave functions with an applied uniform electric field Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg

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Vibrational spectra (matrix and vapour phase) and molecular force field of OVCl3

Cited by 29 publications

References 22 publications

Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Matrix Isolation Study of the Thermal and Photochemical Reaction of OVCl₃ with NH₃: Spectroscopic and Theoretical Characterization of Cl₂V(O)NH₂

Vibrational frequencies of transition metal chloride and oxo compounds using effective core potential analytic second derivatives

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Vibrational spectra (matrix and vapour phase) and molecular force field of OVCl3

Cited by 29 publications

References 22 publications

Matrix Isolation and Density Functional Study of the Reaction of OVCl3 with CH3OH: Synthesis and Characterization of Cl2V(O)OCH3

Matrix Isolation and Density Functional Study of the Reaction of OVCl3 with CH3OH: Synthesis and Characterization of Cl2V(O)OCH3

Matrix Isolation Study of the Thermal and Photochemical Reaction of OVCl3 with NH3: Spectroscopic and Theoretical Characterization of Cl2V(O)NH2

Vibrational frequencies of transition metal chloride and oxo compounds using effective core potential analytic second derivatives

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Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH: Synthesis and Characterization of Cl₂V(O)OCH₃

Matrix Isolation Study of the Thermal and Photochemical Reaction of OVCl₃ with NH₃: Spectroscopic and Theoretical Characterization of Cl₂V(O)NH₂