Studies of the vapor phase photodissociation of azomethane-d(6)

The photodissociation of fully deuterated azomethane into two CD$\sb3$ radicals and N$\sb2$ was studied using transient CARS spectroscopy as a nanosecond resolved probe of the photoproducts. The Raman-active $\nu\sb1$ symmetric C-D stretching band of CD$\sb3$ radicals was observed and the following spectroscopic constants were obtained: $\nu\sb0$ = 2157.5 cm$\sp{-1}$, $\Delta$B = $-$0.026 cm$\sp{-1}$, $\Delta$C = $-$0.018 cm$\sp{-1}$, and X$\sb{12}$ = $-$5 cm$\sp{-1}$. Kinetic observations of the CD$\sb3$ photoproducts indicated that azomethane-d$\sb6$ photodissociates in a stepwise manner through a methyldiazenyl-d$\sb3$ radical intermediate. Indirect observations showed that this intermediate was formed promptly and found to have a lifetime of approximately 7 ns before decomposing into a CD$\sb3$ radical and N$\sb2$. A spectroscopic examination of N$\sb2$ photofragments revealed that their nascent vibrational distribution was 92 $\pm$ 5% in v = 0, 8 $\pm$ 5% in v = 1, and 0 + 5% in v $>$ 1.

Name thesis:degree_name

Master of Arts

Level thesis:degree_level

Masters

Discipline thesis:degree_discipline

Natural Sciences

Grantor

Rice University

Year dc:date.issued

1990

Author dc:creator

• Miller, James Thomas

Advisor dc:contributor.advisor

• Weisman, R. Bruce

• Physical chemistry
• Organic chemistry

Statement dc:rights

• Copyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1911/13454

OAI identifier oai:identifier

oai:repository.rice.edu:1911/13454