Accession Number:

ADA255642

Title:

Electronically Excited Molecules: Reaction Kinetics and Emission of Light: Nanosecond Infrared Spectroscopy, Electronic Emission from Chemical Reactions

Descriptive Note:

Final rept. 1 Nov 1986-15 Apr 1991

Corporate Author:

CALIFORNIA UNIV BERKELEY DEPT OF CHEMISTRY

Personal Author(s):

Report Date:

1992-02-24

Pagination or Media Count:

6.0

Abstract:

A time-resolved IR absorption spectrometer capable of detecting chemical transients on the nanosecond timescale was designed, constructed, and successfully implemented. The spectrometer was used to characterize the vibrational relaxation of an open shell radical species, CF3, produced with excess energy from the photolysis of the parent CF3I compound. The effects of vibrational excitation in the CF3 radical on the reaction CF3 Br2 yields CF3Br Br were measured. Broadband data collection techniques were used to monitor the reactive and relaxation pathways simultaneously. The energetic radicals react no faster than the thermalized CF3 and may actually have a lower cross section for reaction. The spectrometer was also used to detect the gas phase absorption spectra of the polyatomic radicals. A thorough investigation into ozone-olefin reactions in a cryogenic matrix environment was completed. It was possible to complex ozone with various olefinic partners through careful control of the matrix deposition process, despite the very low 1-5 kcalmole activation energies for the ozonolysis reactions. The ground state complexes were observed to form a charge-transfer CT complex upon excitation.

Subject Categories:

  • Organic Chemistry
  • Physical Chemistry
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE