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Weisman, R. Bruce Miller, James Thomas 2009-06-04T00:00:06Z 2009-06-04T00:00:06Z 1990 Miller, James Thomas. "Studies of the vapor phase photodissociation of azomethane-d(6)." (1990) Master’s Thesis, Rice University. <a href="https://hdl.handle.net/1911/13454">https://hdl.handle.net/1911/13454</a>. https://hdl.handle.net/1911/13454 Thesis Chem. 1990 Miller 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. 84 p. application/pdf eng 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. Physical chemistry Organic chemistry Studies of the vapor phase photodissociation of azomethane-d(6) Thesis Text Chemistry Natural Sciences Rice University Masters Master of Arts open.access