Deuteration Affects the Photodissociation of Formaldehyde Open Access

Shearouse, James Craig (2009)

Permanent URL: https://etd.library.emory.edu/concern/etds/kk91fm03m?locale=en
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Abstract


Abstract
Deuteration Affects the Photodissociation of Formaldehyde

By James Craig Shearouse
The effect of mass in the phenomenon of formaldehyde roaming is investigated by the
substitution of a single deuterium to determine whether the proton or the deuteron is more
likely to roam. Possible issues with the preparation of the initial conditions for a
physically accurate and meaningful quasiclassical trajectory simulation of formaldehyde
photodissociation are explored in light of the proposed intramolecular relaxation
mechanism, and a microcanonical sampling method is utilized. Additionally, an
investigation is made as to whether the roaming phenomenon is associated with its own
transition state or whether it is, as hypothesized, a barrierless process. The results of
quasiclassical trajectory simulation of the deuterated system are compared to the
predictions made by a phase space theory/RRKM theory prediction of product
distributions.

Table of Contents



Table of Contents

1. Introduction
pg. 1
2. Phase Space/RRKM Theory Predictions
pg. 4
3. Quasiclassical Trajectory Simulation
pg. 9
4. Detecting Roaming
pg. 12
5. Stationary Point Search
pg. 16
6. Results and Discussion
pg. 18
7. Conclusions
pg. 21
List of Figures

Fig. 1 Lifetimes of all Trajectories Starting from "Stretched Formaldehyde"
pg. 26
Fig. 2 Lifetimes of H+HCO Trajectories Starting from "Stretched Formaldehyde" pg. 27
Fig. 3 Lifetimes of H2+CO Trajectories Starting from "Stretched Formaldehyde" pg. 28
Fig. 4 HD Vibrational Distribution from 37000 cm-1 Photodissociation
pg. 29
Fig. 5 H2 Vibrational Distribution from 37000 cm-1 Photodissociation
pg. 30
Fig. 6 C-H Bond Length during a Roaming D Trajectory, Example 1
pg. 31
Fig. 7 C-D Bond Length during a Roaming D Trajectory, Example 1
pg. 32
Fig. 8 C-H Bond Length during a Roaming D Trajectory, Example 2
pg. 33
Fig. 9 C-D Bond Length during a Roaming D Trajectory, Example 2
pg. 34
Fig. 10 Comparison of H2 and HD Vibrational Distributions
pg. 35
Fig. 11 Comparison of CO Vibrational Distributions from H2CO and HDCO
pg. 36

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