Photochemical Sciences Ph.D. Dissertations

Title

Ultrafast Photochemistry of Polyhalogenated Methanes and Non-Metals

Date of Award

2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Photochemical Sciences

First Advisor

Alexander Tarnovsky (Advisor)

Second Advisor

Haowen Xi (Other)

Third Advisor

Marshall Wilson (Committee Chair)

Fourth Advisor

Alexey Zayak (Committee Chair)

Abstract

A molecular level understanding of photodynamics in condensed media is one of the recent challenges to chemical physics. This is because of the intrinsic complexity of liquid-phase photophysical and photochemical singularities arising from competing intra- and intermolecular processes. Such processes often take place on a timescale of a few femtoseconds (10-15 s) to several tens of picoseconds (10-12 s). In this work, the model photochemical processes used to investigate ultrafast photo-induced reaction dynamics in solution. The model compounds are non-metal/metal polyhalogenated small molecules. The gas-phase photochemistry of these small molecules is thoroughly examined, which also enables to establish the connection between liquid and gas phase dynamics. Furthermore, contrary to the scrupulously investigated di- and triatomic molecular systems, more vibrational degrees of freedom are accessible both for the model parent molecules, nascent polyatomic radical species, and isomer photoproducts. Therefore, a detailed mapping of the photochemical reaction paths of these molecular systems can possibly reveal different couplings between the reactive modes and other dark states in a far-from-equilibrium situation. The complexity of the encountered ultrafast events requires the utilization of several experimental and computational approaches. Results of femtosecond transient absorption, picosecond transient resonance Raman, excited state ab initio calculations are discussed in this context.

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