Photodecomposition of Methyl Nitrite Trapped in Solid Argon
Abstract
The threshold wavelength for the photolysis of methyl nitrite isolated in solid argon at 14 deg K has been determined to be near 370 nm. Photolyzed samples show prominent infrared absorptions of H2CO and HNO, which are perturbed by the hydrogen-bonding interaction of these two molecules trapped in adjacent sites. In studies with 122- an 105-nm radiation sources and with concurrent deposition and photolysis, some of the H2CO escapes interaction with HNO. Similar observations result on photolysis of methyl-d3 nitrite. Time dependence studies show that in the early stages of photolysis the trans-CH3ONO absorptions grow at the expense of those of the cis rotamer. The stabilization of H2CO and HNO is consistent with gas-phase observations, which have demonstrated that the primary products of the photodecomposition of both cis- and trans-CH3ONO are CH3O + NO, which can recombine with zero activation energy either to re-form CH3ONO or to form H2CO + HNO. The cage recombination of CH3O and NO to form these same products should predominate in the decomposition of methyl nitrates in other condensed-phase systems. The possible deactivation of electronically excited methyl nitrite into lower electronic states or into excited vibrational levels of the ground electronic state which favor direct decomposition into H2CO + HNO is considered.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jul 22, 1982
- Accession Number
- ADA119040
Entities
People
- Frederick L. Rook
- Marilyn E. Jacox
Organizations
- National Institute of Standards and Technology