Date of Award

Spring 2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Reid, Scott A.

Second Advisor

Rathore, Rajendra

Third Advisor

Timerghazin, Qadir

Abstract

As time goes by and new innovations are brought up to improve living conditions, the human impact on the environment becomes more significant. It has been shown that man-made halogenated compounds play a key role in many real-world chemical processes. For example, in combustion, these compounds are used as fire retardant agents, and in atmospheric chemistry, they initiate ozone depletion reactions.

However little is known about the mechanisms governing these processes and many intermediates involved in these processes have been elusive to researchers for diverse reasons such as short lifetime and difficulty in distinguishing products from parents molecules. The studies compiled in this work are focused on exploring the photochemical behavior of various intermediates derived from polyhalogenated compounds. These intermediates are trapped in inert rigid matrix and characterized by using IR, UV/Vis spectroscopy supported by computational methods. The photochemistry is explored using selected wavelength appropriate to each species. In this work, the photolysis products of CF2I2, CF2Br2, CXBr3 (X=H, D, F), C2H4Br2, C2F4Br2 have been generated and trapped in Argon or Neon matrices and most of them were characterized for the first time. We have also studied weakly bound complexes (C2H4***Br2, C2H4***I2), formed in matrix by co-deposition of monomers or by trapping fragments resulting from high voltage discharge (H2CXBr***Br; X=H, Cl, Br). We hope that our results will contribute to better understand the photochemical behavior of polyhalogenated species, and to some extent help to understand mechanism in different phenomena involving these species.

Included in

Chemistry Commons

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