Electron paramagnetic resonance study of copper halide tetrazole complexes and the free radicals in irradiated strontium acetate hemihydrate

Loading...
Thumbnail Image
Authors
Gisch, Robert Gary
Subjects
Strontium acetate hemihydrate
Electron paramagnetic resonance
Tetrazoles
Copper halide
Radiation damage
Advisors
Tolles, William M.
Date of Issue
1969-06
Date
June 1969
Publisher
Monterey, California. U.S. Naval Postgraduate School
Language
en_US
Abstract
An EPR study of copper halide tetrazole complexes and x-irradiated strontium acetate hemihydrate has been made. The powder spectra of some of the tetrazole complexes exhibited temperature dependent narrowing and broadening. The one-electron population of the copper d orbital involved in bonding to 2-methy l-5-amino tetrazole has been found to be 0.56 and 0.47, respectively for the chloride and bromide complexes. The g value for these two complexes are consistent with the proposed planar polymeric structure for 2-substituted tetrazole- copper complexes. The species present in single crystals of strontium acetate hemihydrate irradiated and observed at liquid nitrogen temperature to -100 C has a spectrum of four lines of 1:3:3:1 intensity ratio and aCH3 = 11.0 gauss. Temperature dependent exchange behavior of the spectrum for this species is observed and attributed to a rotating methyl group which was found to have 6H# = 3.0 + 0.3 kca l and 6S# = 6.0 + 0.3 cal/mole deg for internal rotation. The species present at room temperature has an eight line spectrum consisting of two 1:3:3:1 intensity ratio patterns with a CH3 = 25.2 and aH - 21.3 gauss. Molecular orbital calculations using the CNDO approximation were performed and possible fragments responsible for these spectra are suggested. 25.2 and a = 2 1 . 3 gaus s . Molecular orbital calculations using the CNDO An EPR study of copper halide tetrazole complexes and x- irrad iated strontium acetate hemihydrate has been made. The powder spectra of some of the tetrazole complexes exhibited temperature dependent narrowing and broadening. The one-elec tron populat ion of the copper d orbital involved in bonding to 2-methy l-5-amino tetrazole has been found to be 0.56 and 0.47, respec tively for the chloride and bromide complexes. The g value for these two complexes are consistent with the proposed planar poly- meric structure for 2-substituted tetrazole- copper complexes. The species present in single crystals of strontium acetate hemihydrate ir- 0 radiated and observed at liquid nitrogen temperature to -100 C has a spectrum of four lines of 1:3:3:1 intensity ratio and aCH3 = 11.0 gauss. Temperature dependent exchange behavior of the spectrum for this species is observed and attributed to a rotating methyl group which was found to have 6H# = 3.0 + 0.3 kca l and 6S# = 6.0 + 0.3 cal/mole deg for internal - mole rotation. The species present at room temperature has an eight line spectrum consisting of two 1:3:3:1 intensity ratio patterns with aCH3 = H 25.2 and a = 2 1 . 3 gaus s . Molecular orbital calculations using the CNDO
Type
Thesis
Description
Series/Report No
Department
Chemistry
Organization
Naval Postgraduate School (U.S.)
Identifiers
NPS Report Number
Sponsors
Funder
Format
Citation
Distribution Statement
Approved for public release; distribution is unlimited.
Rights
This publication is a work of the U.S. Government as defined in Title 17, United States Code, Section 101. Copyright protection is not available for this work in the United States.
Collections