Influence of Reactant Structure and Secondary Reactions on H2O 010/000 Vibrational Populations Produced via OH + Cycloalkanes

Simianu, Valerian C.; Viegut, Terrance R.; Lindberg, Cristy M.; Hossenlopp, Jeanne M.

doi:10.1021/j100025a024

Cited by 3 publications

(2 citation statements)

References 13 publications

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“…Consequently, the fitting errors are less than 10%. The better fitting is explained by the use of a more accurate fundamental (001) emission band; some line intensities in the H 2 O emission fundamental band may be incorrect by a factor of 3 × 3 = 9 because the wrong assignment of a statistical factor, g , in an initial absorption band (this kind of error for some HITRAN lines was also indicated in ref b).…”

Section: Resultsmentioning

confidence: 99%

“…The v = 0 populations were estimated with the help of surprisal analysis; inverted distributions were obtained in the stretching modes for all reactions. Up to now, the only observation of vibrational excitation of H 2 O from abstraction reactions was made by time-resolved, infrared diode laser absorption/gain spectroscopy in the reaction of OH with cyclooctane . Population inversions were observed for the 010, 020, and 100 levels of H 2 O.…”

Section: Introductionmentioning

confidence: 99%

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Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr

and

Setser

1996

J. Phys. Chem.

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Infrared chemiluminescence from vibrationally excited H 2 O, HOD, and D 2 O molecules in the ranges 3200-3900 cm -1 (O-H stretch) and 2400-2900 cm -1 (O-D stretch) was observed from the reactions of OH and OD radicals with hydrogen and deuterium bromide in a fast flow reactor with 0.5-2 Torr of Ar carrier gas at 300 K. Hydroxyl radicals were produced via the H + NO 2 reaction; the H atoms were generated by microwave discharge in a H 2 /Ar mixture. Vibrational distributions for H 2 O, HOD, and D 2 O were determined by computer simulation of the experimental emission spectra. The H 2 O emission from OH + HBr reaction shows inverted populations for both the collisionally coupled stretching modes and the bending mode. Inversion in the bending distribution with a maximum for V 2 ) 1 is more apparent in the V 1,3 ) 1 level, which is populated up to the thermochemical limit of V 2 ) 5. The HOD emission from OD + HBr shows an inverted population in the O-H stretching mode with a maximum for V 3 ) 2 and shows a decreasing population in the collisionally mixed O-D stretching/bending ν 1,2 levels with half the molecules in the V 1 ) 0 group. The distribution in ν 1,2 for HOD from the OH + DBr reaction also appeared to be decreasing for V 1 > 0 levels, but collisional redistribution to V 3 ) 1 seems evident from the pressure dependence of the vibrational distributions. These distributions are discussed with the aid of the information theoretic analysis and compared to F atom abstraction reactions from HBr and DBr and to quantum-scattering calculations on an OH + HBr surface. The overall vibrational energy disposal is 〈f V 〉 ≈ 0.6, which resembles the analogous three-body cases. However, the partitioning of the energy between stretching and bending modes raises new questions about reaction dynamics.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr

and

Setser

1996

J. Phys. Chem.

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Detection of benzaldehyde and formaldehyde in the UV photolysis of gas-phase methyl benzoate

Christophy

Myli

Viegut

et al. 1997

Journal of Photochemistry and Photobiology A: Chemistry

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Vibrational excitation of H2O and HOD molecules produced by reactions of OH and OD with cyclo-C6H12, n-C4H10, neo-C5H12, HCl, DCl and NH3 as studied by infrared chemiluminescence

Butkovskaya

Setser

1998

The Journal of Chemical Physics

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The room-temperature reactions of OH(OD) radicals with cyclo-C6H12, n-C4H10, and neo-C5H12 have been investigated by observing the infrared chemiluminescence from the H2O(HOD) molecules generated in a fast-flow reactor. These hydrocarbon molecules are representative for abstraction from secondary and primary C–H bonds. The total vibrational energy released to H2O(HOD) was in the range of 〈fv〉=0.55–0.65. The majority (80%–85%) of the vibrational energy is in the stretching modes and the main energy release is to the local mode associated with the new OH bond. The dynamics associated with the energy disposal to H2O(HOD) resemble the H+L−H dynamics for the analogous reactions of F atoms. The data from H2O and HOD are complementary because of the different collisional coupling between the energy levels of the ν1, ν2, and ν3 modes; however, no specific isotope effect was found for the energy disposal to H2O versus HOD for reactions with the hydrocarbon molecules. In contrast, a very unusual isotope effect was found between the OH+HCl and OD+HCl pairs. The latter reaction gave the expected stretching mode excitation of HOD; however, the OH reaction gave H2O molecules with virtually no vibrational energy. This anomalous situation is partly associated with an inverse secondary kinetic-isotope effect, but the main isotope effect is on the dynamics of the energy disposal process itself.

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Influence of Reactant Structure and Secondary Reactions on H2O 010/000 Vibrational Populations Produced via OH + Cycloalkanes

Cited by 3 publications

References 13 publications

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr

Detection of benzaldehyde and formaldehyde in the UV photolysis of gas-phase methyl benzoate

Vibrational excitation of H2O and HOD molecules produced by reactions of OH and OD with cyclo-C6H12, n-C4H10, neo-C5H12, HCl, DCl and NH3 as studied by infrared chemiluminescence

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Influence of Reactant Structure and Secondary Reactions on H2O 010/000 Vibrational Populations Produced via OH + Cycloalkanes

Cited by 3 publications

References 13 publications

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H2O, HOD, and D2O Produced in Reactions of OH and OD with HBr and DBr

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H2O, HOD, and D2O Produced in Reactions of OH and OD with HBr and DBr

Detection of benzaldehyde and formaldehyde in the UV photolysis of gas-phase methyl benzoate

Vibrational excitation of H2O and HOD molecules produced by reactions of OH and OD with cyclo-C6H12, n-C4H10, neo-C5H12, HCl, DCl and NH3 as studied by infrared chemiluminescence

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Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr

Chemical Dynamics of H Abstraction by OH Radicals: Vibrational Excitation of H₂O, HOD, and D₂O Produced in Reactions of OH and OD with HBr and DBr