Cart
Article
Spectra and Photochemistry of Trifluoronitrosomethane Adsorbed on Alkali Halide Films
Full Text HTML
Hi-Res PDFPurchase the full-text
- PDF/HTML,
figures/images,
references and tables,
(where available)
Janine M. Rusnock, and Christopher A. Baumann*Abstract
Trifluoronitrosomethane (CF3NO), which is readily photolyzed in the gas phase when exposed to light in the 600−700 nm portion of the spectrum, does not undergo significant photolysis when irradiated while adsorbed on sublimated films of alkali halides (NaCl, NaBr, KCl, KBr) at temperatures of 10−100 K. This quenching does not occur when the molecule is irradiated while adsorbed on argon films (thickness > 0.1 μm) or in multilayer coverage. Comparison of the quantum efficiencies for photolysis indicates that vibrational relaxation induced by surface phonons is primarily responsible for the alkali halide quenching, but lateral diffusion of the photofragments and/or excited-state molecules may also play a role in the kinetic scheme. The photochemistry was followed using infrared spectroscopy, providing the first vibrational characterization of adsorbed sub-monolayer CF3NO. A photodimer of CF3NO was also observed and vibrationally characterized on the argon films and on the overlayers. The NO stretching frequency for the dimer is significantly lower than had been previously reported for the N-nitritoamine photodimer {(CF3)2NONO} and may indicate the existence of a second photodimer species. Adsorption potentials were calculated for various sites on the four alkali halide films. The lowest energy orientation in each case had the C−N bond parallel to the surface, aligned in the [110] direction. The vibrational spectra and thermal desorption curves are consistent with the calculated energies.
Citing Articles
Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.
This article has been cited by 2 ACS Journal articles (2 most recent appear below).
Matrix Isolation and Density Functional Theory Study of Bis(trifluoromethyl)dioxodiazine: A Photodimer of Trifluoronitrosomethane
Brendan C. Haynie, Megan J. Morgan, and Christopher A. BaumannThe Journal of Physical Chemistry A2005 109 (24), 5307-5315Matrix Isolation and Density Functional Theory Study of Bis(trifluoromethyl)dioxodiazine: A Photodimer of Trifluoronitrosomethane
Brendan C. Haynie, Megan J. Morgan, and Christopher A. BaumannThe Journal of Physical Chemistry A2005 109 (24), 5307-5315Trifluoronitrosomethane (CF3NO) was trapped in rare gas matrixes and irradiated at 633 and 670 nm. The infrared spectra of the postirradiation samples exhibit features consistent with cis and trans conformers of bis(trifluoromethyl)dioxodiazine, a ...
Spectra and Photochemistry of Trifluoronitromethane Adsorbed on Alkali Halide Films
Mariaelena Galie, Janine M. Rusnock, Michael E. Yevich, and Christopher A. BaumannThe Journal of Physical Chemistry B1997 101 (41), 8304-8314Spectra and Photochemistry of Trifluoronitromethane Adsorbed on Alkali Halide Films
Mariaelena Galie, Janine M. Rusnock, Michael E. Yevich, and Christopher A. BaumannThe Journal of Physical Chemistry B1997 101 (41), 8304-8314The infrared spectrum of trifluoronitromethane (CF3NO2) physically adsorbed on sublimated alkali halide (NaCl, NaBr, KCl, and KBr) films in submonolayer and multilayer coverages, and isolated in argon and nitrogen matrices, has been observed. The ...
Tools
-
Add to Favorites
-
Download Citation
-
Email a Colleague -
Permalink
Order Reprints
Rights & Permissions
Citation Alerts
SciFinder Links
Explore by:
History
- Published In Issue September 19, 1996
- Received April 8, 1996
Revised July 15, 1996
ACS
Network
Facebook
Tweet This
CiteULike
Newsvine
Digg This
Delicious
