Date of Award

2016

Document Type

Thesis

Degree Name

Bachelors

Department

Natural Sciences

First Advisor

Shipman, Steven

Area of Concentration

Chemistry

Abstract

We present direct rate constant measurements for the reaction of CH2OO+ISP using time resolved cavity enhanced absorption spectroscopy of CH2OO’s B1A’ ← X1A’ transition. We found the reaction to be pressure independent between 15-100 torr and temperature dependent between 296-536 K. Rate constants vary from (1.6±0.1) to (20±2.0) x 10-15 cm3 molec-1 s-1, but exhibit a curved Arrhenius behavior. We extract estimated activation energies, which range from Ea=5.7 kJ mol-1 at room temperature to Ea=40.3 kJ mol-1 at higher temperatures. Quantum chemical calculations of 16 CH2OO+ISP transition states provide transitions state ZPE-inclusive barriers and product wells.

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