Accession Number:

ADA285223

Title:

Metastability in Molecules

Descriptive Note:

Annual rept. 1993

Corporate Author:

FLORIDA UNIV GAINESVILLE

Personal Author(s):

Report Date:

1994-09-08

Pagination or Media Count:

13.0

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 CCSDT calculations to characterize carbonyl oxide. These studies employed recently developed open-shell analytical gradients methods for CCSDT, 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 kcalmol. CCSDT 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

Subject Categories:

  • Organic Chemistry
  • Physical Chemistry
  • Atomic and Molecular Physics and Spectroscopy
  • Quantum Theory and Relativity

Distribution Statement:

APPROVED FOR PUBLIC RELEASE