Metastability in Molecules
Abstract
Synthesis and detonation of energetic materials involves several critical oxidation processes and associated intermediates. Carbonyl oxide, and its cyclic isomeric form, dioxirane, are two key compounds in such processes. Carbonyl oxide has never been observed experimentally, though it is one of the most discussed compounds awaiting detection. We performed high level coupled- cluster CCSD(T) calculations to characterize carbonyl oxide. These studies employed recently developed open-shell analytical gradients methods for CCSD(T), without which structures and vibrational frequencies would be difficult to obtain. The Delta H sub f deg (298) for carbonyl oxide is found to be 30.2 kcal/ mol, while the barrier to isomerization to dioxirane is 19.2 kcal/mol. CCSD(T) vibrational frequencies of both species are presented to facilitate identification along with the 18 O isotope shifts. Shifts as high as 45 /cm permit experimental discrimination between the two forms. Carbonyl oxide is found to be far more zwitterionic than lower level theoretical studies would suggest, in line with the viewpoint of synthetic chemists
Document Details
- Document Type
- Technical Report
- Publication Date
- Sep 08, 1994
- Accession Number
- ADA285223
Entities
People
- Rodney J. Bartlett
Organizations
- University of Florida