Mid- and Far-Infrared Spectra of HF and DF in Rare-Gas Matrices

Mason, M. G.; Holle, W.G. Von; Robinson, Dean W.

doi:10.1063/1.1675371

Cited by 79 publications

(6 citation statements)

References 21 publications

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“…Also a weak absorption of the HCO radical could be identified. An unassigned absorption at 3886.53 cm -1 was red shifted from the monomeric HF absorption, which most probably belongs to the HF complex, but there was no counterpart in the CO stretching region. As in the krypton matrix, the CO/HF species dissociate in the xenon matrix at both photolysis wavelengths.…”

Section: Resultsmentioning

confidence: 94%

“…The absorption at 3932.31 cm -1 is assigned to nonrotating monomeric HF, and the absorptions at 1853.04 and 1852.36 cm -1 most probably belong to the FCO radical. − The group of peaks at 1938, 1910, 1235, 964, and 766 cm -1 are assigned to the F 2 CO molecule . The absorption at 852.45 cm -1 has been assigned to the ionic Kr 2 H + species, and the absorption at 2342 cm -1 belongs to CO 2 .…”

Section: Resultsmentioning

confidence: 99%

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Photodissociation of Formyl Fluoride in Rare Gas Matrixes

2006

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Photodissociation of formyl fluoride (HCOF) is studied in Ar, Kr, and Xe matrixes at 248 and 193 nm excitation by following spectral changes in the infrared absorption spectra. In all matrixes, the main photodissociation products are CO/HF species, including CO-HF and OC-HF complexes and thermally unstable CO/HF species (a distorted CO/HF complex or a reaction intermediate), which indicate negligible cage exit of atoms produced via the C-F and C-H bond cleavage channels. However, the observation of traces of H, F, CO, CO(2), F(2)CO, FCO, and HRg(2)(+) (Rg = Kr or Xe) in Kr and Xe matrixes would imply some importance of other reaction channels too. The analysis of the decay curves of the precursor shows that dissociation efficiency of HCOF increases as Ar < Kr < Xe, the difference being the factor of 10 between Ar and Xe. Moreover, HCOF dissociates 20-50 times faster at 193 nm compared to 248 nm. Interestingly, whereas the CO/HF species are stable with respect to photolysis in Ar, they photobleach in Kr and Xe matrixes at 248 and 193 nm, even though the first excited states of CO and HF are not energetically accessible with 193 and 248 nm photons. In krypton matrix, the photodissociation of CO/HF species at 248 nm is observed to be a single photon process. Quantum chemical calculations of electronic excitation energies of CO-HF and OC-HF complexes show that the electronic states of HF and CO mostly retain their diatomic nature in the pair. This clearly demonstrates that photodissociation of CO/HF complexes is promoted by the surrounding rare gas lattice.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Photodissociation of Formyl Fluoride in Rare Gas Matrixes

2006

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“…It is clear from the comparison of the lists of EB‐MI products, and the ionic products in the PEPICO‐based results, that these two sets are not the same. Specifically, no observation of matrix isolated vinyl radical (C 2 H 3 • ) is observed,14, 15 nor the matrix isolated HF monomer,16, 17 nor freely isolated C 2 H 2 7. However, the products of both techniques are very closely related and can be rationalized by considering the differences in experimental conditions of the two techniques.…”

Section: Discussionmentioning

confidence: 96%

Electron‐bombardment matrix isolation and PEPICO studies as complementary techniques in ion chemistry: an FTIR study of the decomposition of the vinyl fluoride cation

Thompson¹,

Linford²,

Parnis³

2011

J. Mass Spectrom.

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FTIR spectra have been obtained for matrices formed following electron bombardment of gas mixtures containing varying amounts of vinyl fluoride (VF) in Ar (1:400 to 1:25,600; VF/Ar). The major matrix-isolated products are a π-complex of HF/C(2)H(2) , fluoroacetylene (HC≡CF) and two isomers of C(2)H(2)F(•). These products correspond well with the products of photoionization of VF near 15.8 eV. These observations support the dominant mechanism of ionization in the EB-MI environment as charge transfer of the substrate molecule to Ar(•+). Some differences are noted between the observed EB-MI products and the results from PEPICO studies, primarily in that the EB-MI products are observed as neutralized forms. The close correlation in EB-MI and photoionization results allows the EB-MI technique to be utilized as an ion structural analysis tool in complement to PEPICO studies, and allows the use of PEPICO studies to help predict and elucidate high-pressure chemistry mechanisms through EB-MI studies. The differences in the EB-MI results and ions observed using the PEPICO technique are rationalized in terms of the differences in the experimental techniques. Using VF as the test system, reagent partial pressure conditions that best complement PEPICO studies are determined. Although the major results are observed for all VF partial pressures, dilute samples give rise to further ionization of the primary products, and more concentrated samples give rise to radical-radical reaction chemistry. As a result, a nominal range of 1:3200 (VF/Ar) is demonstrated to provide the best correlation with the gas-phase PEPICO measurements.

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“…Inert-gas matrices have proven to be very useful (for example, References [32][33][34][35][36]) for studying molecules trapped within them-particularly reactive molecules, since the individual molecules can be isolated by the matrix. Because the lattice is transparent, the trapped molecules can be excited with lasers and fluorescence can be observed.…”

Section: The Study Of Molecules Trapped In An Inert-gas Solidmentioning

confidence: 99%

Oriented Polar Molecules in a Solid Inert-Gas Matrix: A Proposed Method for Measuring the Electric Dipole Moment of the Electron

Vutha

Horbatsch

Hessels

2018

Atoms

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Abstract:We propose a very sensitive method for measuring the electric dipole moment of the electron using polar molecules embedded in a cryogenic solid matrix of inert-gas atoms. The polar molecules can be oriented in theẑ-direction by an applied electric field, as has recently been demonstrated by Park et al. The trapped molecules are prepared into a state that has its electron spin perpendicular tô z, and a magnetic field alongẑ causes precession of this spin. An electron electric dipole moment d e would affect this precession due to the up to 100 GV/cm effective electric field produced by the polar molecule. The large number of polar molecules that can be embedded in a matrix, along with the expected long coherence times for the precession, allows for the possibility of measuring d e to an accuracy that surpasses current measurements by many orders of magnitude. Because the matrix can inhibit molecular rotations and lock the orientation of the polar molecules, it may not be necessary to have an electric field present during the precession. The proposed technique can be applied using a variety of polar molecules and inert gases, which, along with other experimental variables, should allow for careful study of systematic uncertainties in the measurement.

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Mid- and Far-Infrared Spectra of HF and DF in Rare-Gas Matrices

Cited by 79 publications

References 21 publications

Photodissociation of Formyl Fluoride in Rare Gas Matrixes

Photodissociation of Formyl Fluoride in Rare Gas Matrixes

Electron‐bombardment matrix isolation and PEPICO studies as complementary techniques in ion chemistry: an FTIR study of the decomposition of the vinyl fluoride cation

Oriented Polar Molecules in a Solid Inert-Gas Matrix: A Proposed Method for Measuring the Electric Dipole Moment of the Electron

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