DOI: 10.1063/1.467355. Double resonance infrared–visible photofragment yield spectroscopy of NO2: Interferences among overlapping quasibound levels

Double resonance infrared–visible photofragment yield spectroscopy of NO2: Interferences among overlapping quasibound levels

10.1063/1.467355

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We examine fluctuations in the unimolecular decomposition of state-selected NO2 using double resonance infrared (IR)–visible and visible–IR photofragment yield (PHOFRY) spectroscopy. Spectra for specific NO(v,J,Λ,Ω) states at excess energies (E°)=2000–2525 cm−1 exhibit marked differences in the shapes, positions, and widths of the resonance structures. We interpret this effect as arising from interferences among coherently excited overlapping quasibound levels. Comparisons of IR–visible PHOFRY spectra with one-photon spectra in the same energy region and IR–visible spectra at lower E° are used to assess the importance of thermal averaging (i.e., incoherent excitations) and to examine the transition from mild to more severe level overlap. The experimental results are compared qualitatively with results from sample calculations to shed further light on the interplay between dynamics and statistics in the decomposition and the role of overlapping quasibound levels.

Bibliography

Reid, S. A., & Reisler, H. (1994). Double resonance infraredâvisible photofragment yield spectroscopy of NO2: Interferences among overlapping quasibound levels. The Journal of Chemical Physics, 101(7), 5683â5699.

Authors 2

S. A. Reid (first)
H. Reisler (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:12 a.m.)
Deposited	1 year, 6 months ago (Feb. 5, 2024, 2:01 p.m.)
Indexed	1 year, 6 months ago (Feb. 11, 2024, 2:21 a.m.)
Issued	30 years, 11 months ago (Oct. 1, 1994)
Published	30 years, 11 months ago (Oct. 1, 1994)
Published Print	30 years, 11 months ago (Oct. 1, 1994)

Funders 0

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BibTeX

@article{Reid_1994, title={Double resonance infrared–visible photofragment yield spectroscopy of NO2: Interferences among overlapping quasibound levels}, volume={101}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.467355}, DOI={10.1063/1.467355}, number={7}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Reid, S. A. and Reisler, H.}, year={1994}, month=oct, pages={5683–5699} }

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  "abstract": "<jats:p>We examine fluctuations in the unimolecular decomposition of state-selected NO2 using double resonance infrared (IR)\u2013visible and visible\u2013IR photofragment yield (PHOFRY) spectroscopy. Spectra for specific NO(v,J,\u039b,\u03a9) states at excess energies (E\u00b0)=2000\u20132525 cm\u22121 exhibit marked differences in the shapes, positions, and widths of the resonance structures. We interpret this effect as arising from interferences among coherently excited overlapping quasibound levels. Comparisons of IR\u2013visible PHOFRY spectra with one-photon spectra in the same energy region and IR\u2013visible spectra at lower E\u00b0 are used to assess the importance of thermal averaging (i.e., incoherent excitations) and to examine the transition from mild to more severe level overlap. The experimental results are compared qualitatively with results from sample calculations to shed further light on the interplay between dynamics and statistics in the decomposition and the role of overlapping quasibound levels.</jats:p>",
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