{"id":{"repo_id":"rice","oai_identifier":"oai:repository.rice.edu:1911/13454"},"canonical_url":"https://search.dev.ndltd.org/etd/rice/oai:repository.rice.edu:1911/13454","repository":{"repo_id":"rice","name":"Rice University","base_url":"https://repository.rice.edu/server/oai/request"},"display":{"title":"Studies of the vapor phase photodissociation of azomethane-d(6)","abstract":"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.","abstract_html":"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.","abstract_has_math":true,"creators":["Miller, James Thomas"],"institution":"Rice University","degree_name":"Master of Arts","degree_level":"Masters","degree_discipline":"Natural Sciences","degree_department":null,"school":null,"contributors":[],"advisors":["Weisman, R. Bruce"],"committee_chairs":[],"committee_members":[],"year":1990,"date_issued":"1990","date_published":"1990","updated_at":"2026-07-24T04:10:28Z","subjects":["Physical chemistry","Organic chemistry"],"languages":["eng"],"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."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1911/13454","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Weisman, R. Bruce"]},{"key":"dc:creator","label":"Author","values":["Miller, James Thomas"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2009-06-04T00:00:06Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2009-06-04T00:00:06Z"]},{"key":"dc:date.issued","label":"Date","values":["1990"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Natural Sciences"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Arts"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Rice University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Physical chemistry","Organic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["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."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1911/13454"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Studies of the vapor phase photodissociation of azomethane-d(6)"]}]}],"canonical_facts":{"dc:contributor.advisor":["Weisman, R. Bruce"],"dc:creator":["Miller, James Thomas"],"dc:date.accessioned":["2009-06-04T00:00:06Z"],"dc:date.available":["2009-06-04T00:00:06Z"],"dc:date.issued":["1990"],"dc:description.abstract":["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."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/1911/13454"],"dc:language.iso":["eng"],"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."],"dc:subject":["Physical chemistry","Organic chemistry"],"dc:title":["Studies of the vapor phase photodissociation of azomethane-d(6)"],"dc:type":["Thesis"],"thesis:degree_discipline":["Natural Sciences"],"thesis:degree_level":["Masters"],"thesis:degree_name":["Master of Arts"],"thesis:institution_name":["Rice University"]},"updated_at":"2026-07-24T04:10:28Z"}