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Dynamics of the simplest reaction at...

Camden, Jon.

Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom.
Author:	Camden, Jon.
Description:	126 p.
Notes:	Adviser: Richard N. Zare.
Notes:	Source: Dissertation Abstracts International, Volume: 66-04, Section: B, page: 2081.
Contained By:	Dissertation Abstracts International66-04B.
Subject:	Chemistry, Physical.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3171731
ISBN:	0542086123

Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom.
Camden, Jon.

Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom. - 126 p.

Adviser: Richard N. Zare.

Thesis (Ph.D.)--Stanford University, 2005.

We use the photoinitiated reaction technique analyzed by the law-of-cosines (photoloc) to study the dynamics of the hydrogen plus methane reaction under single collision conditions. A comparison between theory and experiment for the benchmark H + CD4 → HD + CD3 abstraction reaction yields a reinterpretation of the reaction mechanism and highlights the unexpected contribution of a stripping mechanism. We find that bent H-D-C transition state geometries play an important role in the dynamics. A simple model that relates the scattering angle impact parameter, and cone of acceptance accounts well for the overall reaction dynamics. We have also investigated the effects of C-H stretching excitation on the H + CH4 → CH3 + H2 reaction. Excitation of the CH 4(nu3 = 1) mode enhances the overall reaction cross section by a factor of 3.0 + 1.5 at a center of mass collision energy of 1.52 eV. This enhancement factor is found to be approximately constant over the 1.52--2.20 eV collision energy range. A local mode description of the CH4 stretching vibration, in which the C-H oscillators are uncoupled, is used to describe the observed state distributions. We further report the methyl radical product state distributions for the reactions of H and Cl with CHD 3(nu1 = 1,2) at a collision energy of 0.17 and 1.5 eV respectively. Both reactions demonstrate mode selectivity. The resulting state distribution from the H + CHD3(nu1 = 1,2) reactions are well described by a spectator picture. The reactions Cl + CHD3(nu1 = 1,2) exhibit similar behavior but in some cases the spectator picture breaks down. We attribute this breakdown to the slower approach of the Cl atom which enables it to perturb the methane vibrational wavefunction.

ISBN: 0542086123Subjects--Topical Terms:

226924
Chemistry, Physical.

Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom.
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245 1 0 $a Dynamics of the simplest reaction at a tetrahedrally bonded carbon atom.
300 $a 126 p.
500 $a Adviser: Richard N. Zare.
500 $a Source: Dissertation Abstracts International, Volume: 66-04, Section: B, page: 2081.
502 $a Thesis (Ph.D.)--Stanford University, 2005.
520 # $a We use the photoinitiated reaction technique analyzed by the law-of-cosines (photoloc) to study the dynamics of the hydrogen plus methane reaction under single collision conditions. A comparison between theory and experiment for the benchmark H + CD4 → HD + CD3 abstraction reaction yields a reinterpretation of the reaction mechanism and highlights the unexpected contribution of a stripping mechanism. We find that bent H-D-C transition state geometries play an important role in the dynamics. A simple model that relates the scattering angle impact parameter, and cone of acceptance accounts well for the overall reaction dynamics. We have also investigated the effects of C-H stretching excitation on the H + CH4 → CH3 + H2 reaction. Excitation of the CH 4(nu3 = 1) mode enhances the overall reaction cross section by a factor of 3.0 + 1.5 at a center of mass collision energy of 1.52 eV. This enhancement factor is found to be approximately constant over the 1.52--2.20 eV collision energy range. A local mode description of the CH4 stretching vibration, in which the C-H oscillators are uncoupled, is used to describe the observed state distributions. We further report the methyl radical product state distributions for the reactions of H and Cl with CHD 3(nu1 = 1,2) at a collision energy of 0.17 and 1.5 eV respectively. Both reactions demonstrate mode selectivity. The resulting state distribution from the H + CHD3(nu1 = 1,2) reactions are well described by a spectator picture. The reactions Cl + CHD3(nu1 = 1,2) exhibit similar behavior but in some cases the spectator picture breaks down. We attribute this breakdown to the slower approach of the Cl atom which enables it to perturb the methane vibrational wavefunction.
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