Photodissociation dynamics of tert-butyl hydroperoxide at 213 nm via degenerate four-wave mixing spectroscopy

Keon Woo Lee, Dong Chan Kim, Kyung Hoon Jung, Jae Won Hahn

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The photodissociation dynamics of t-BuOOH at 213 nm has been studied using degenerate four-wave mixing spectroscopy. The internal energy distribution, Λ-doublet ratio and spin-orbit state ratio of OH (X2∏, υ″ = 0) fragments were extracted. The OH radicals were found to be vibrationally cold with an average rotational energy of 1726 cm-1, indicating that 5.0% of the available energy was transferred into the OH rotational degree of freedom. A Gaussian distribution of product rotational energy was observed. The population was found to be distributed statistically between the two spin-orbit states. A preferential population of the π+ A-doublet was observed irrespective of N without inversion. The observed Λ-doublet nonequilibrium implies that splitting of energy levels may occur because of the breaking of symmetry due to substitution. We suggest that the hydroxyl part should be the dominant chromophore for the absorption of t-BuOOH at 213 nm.

Original languageEnglish
Pages (from-to)1427-1432
Number of pages6
JournalJournal of Chemical Physics
Volume111
Issue number4
DOIs
Publication statusPublished - 1999 Jul 22

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Photodissociation
tert-Butylhydroperoxide
Four wave mixing
four-wave mixing
photodissociation
Orbits
Spectroscopy
Gaussian distribution
Chromophores
Hydroxyl Radical
Electron energy levels
spectroscopy
orbits
Substitution reactions
internal energy
normal density functions
chromophores
energy
energy distribution
degrees of freedom

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Photodissociation dynamics of tert-butyl hydroperoxide at 213 nm via degenerate four-wave mixing spectroscopy",
abstract = "The photodissociation dynamics of t-BuOOH at 213 nm has been studied using degenerate four-wave mixing spectroscopy. The internal energy distribution, Λ-doublet ratio and spin-orbit state ratio of OH (X2∏, υ″ = 0) fragments were extracted. The OH radicals were found to be vibrationally cold with an average rotational energy of 1726 cm-1, indicating that 5.0{\%} of the available energy was transferred into the OH rotational degree of freedom. A Gaussian distribution of product rotational energy was observed. The population was found to be distributed statistically between the two spin-orbit states. A preferential population of the π+ A-doublet was observed irrespective of N without inversion. The observed Λ-doublet nonequilibrium implies that splitting of energy levels may occur because of the breaking of symmetry due to substitution. We suggest that the hydroxyl part should be the dominant chromophore for the absorption of t-BuOOH at 213 nm.",
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Photodissociation dynamics of tert-butyl hydroperoxide at 213 nm via degenerate four-wave mixing spectroscopy. / Lee, Keon Woo; Kim, Dong Chan; Jung, Kyung Hoon; Hahn, Jae Won.

In: Journal of Chemical Physics, Vol. 111, No. 4, 22.07.1999, p. 1427-1432.

Research output: Contribution to journalArticle

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T1 - Photodissociation dynamics of tert-butyl hydroperoxide at 213 nm via degenerate four-wave mixing spectroscopy

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AU - Kim, Dong Chan

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AB - The photodissociation dynamics of t-BuOOH at 213 nm has been studied using degenerate four-wave mixing spectroscopy. The internal energy distribution, Λ-doublet ratio and spin-orbit state ratio of OH (X2∏, υ″ = 0) fragments were extracted. The OH radicals were found to be vibrationally cold with an average rotational energy of 1726 cm-1, indicating that 5.0% of the available energy was transferred into the OH rotational degree of freedom. A Gaussian distribution of product rotational energy was observed. The population was found to be distributed statistically between the two spin-orbit states. A preferential population of the π+ A-doublet was observed irrespective of N without inversion. The observed Λ-doublet nonequilibrium implies that splitting of energy levels may occur because of the breaking of symmetry due to substitution. We suggest that the hydroxyl part should be the dominant chromophore for the absorption of t-BuOOH at 213 nm.

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