DTIC ADA262819: Cationic Polymerization within Clusters Composed of Unsaturated Molecules

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by  Defense Technical Information Center

AD-A262 819 OFFICE OF NAVAL RESEARCH
III'll I l GIRANT N00014-88-K-0483
R & T Code 413n008
Technical Report No. 38
Cationic Polymezation Wthin
Clusters Composed of Unsaturated Molecules
by
M. Thdd Coolbaugh, Gopal Vaidyanathan and James F. Garvey*
Prepared for Publication
in
International Reviews of Physical Chemistry
Acheson Hall
Department of Chemistih
University at Buffalo
The State University of New Ybrk at Buffalo
Buffalo, NY S
D IC
14214
(cid:127)g(cid:127)ft
April 3. 1993 PR 1 3
Reproduction in whole or in part is permitted for any purpose of the United
States Government
This document has been approved for public release and sale, its distribution
is unlimited
1EForm
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1. AGENCY USE ONLY (Leave blank) Tj2RE PORT DATE 3. REPORT TYPE AND DATES COVERED
4 /3/1993 Technical
4. TITLE AND SUBTITLE S. FUNDING NUMBERS
Cationic Polymerization within Clusters Composed of R & T Code:
Unsaturated Molecules
4 13n008
6. AUTHOR(S)
M. Todd Coolbaugh, Gopalakrishnan Vaidyanathan and
James F. Garvey G N00014-88-K-0483
7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION
Dept. of Chemistry, Acheson Hall REPORT NUMBER
State University of New York at Buffalo Technical Report
Buffalo, NY #38
142 )4
9. SPONSORING /MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING /MONITORING
Dr. R. DeMarco/Dr. J. Pazik, Chemistry Division AGENCY REPORT NUMBER
Office of Naval Research
800 N. Quincy St.
Arlington, VA
22217
11. SUPPLEMENTARY NOTES 93-07541 @
1111
11
IMIl l! IIIIi iU! II/lI
_________________________________IIlIIII _____________
i'iJIiIIlhIIIhIIIIIJJ
12a. DISTrIBUTION /AVAILABILITY STATEMENT rioN CODE
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Approved for public release;
distribution unlimited
13. ABSTRACT (Maximum 200 words)
Electron impact ionization of large neutral clusters composed of simple olefinic
molecules (ethene, 1,1-difluoroethene and propene) display highly anomalous ion in-
tensity distributions. These cluster ion distributions typically exhibit a magic
number at n=4, for cluster ions of the type {M}n+, where M is an olefinic molecule.
The explanation which best explains this observation is that these small 'cluster'
ions are in actuality covalently bound molecular ions formed by sequential ion-
molecule association (polymerization) reactions which have occurred within the clus-
ter ion. This size dependent cluster chemistry is accounted for by kinetic bottle-
necks which occur in the ionic chain growth reactions and which terminate with the
formation of cyclic molecular ions (i.e. cyclopentanes and cyclohexanes ions). The
condensed phase counterparts of these intracluster reactions are the free cationic
polymerization reactions initiated by radiolysis of bulk samples of the olefins. In
addition to reviewing our own efforts in this field, we will discuss previous work
on cationic polymerization which is relevant to the new chemistry we have observed
within clusters of olefinic molecules. We also will present work concerning acety-
lene and methylacetylene cluster ions where we also observe similar intra-cluster...
14. SUBJECT TERMS "IS NUMBER OF PAGES
IS. PRICE CODE
17. SECURITY CLASSIFICATION I1. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACT
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