Primary Processes in the Photolysis of NO<sub>2</sub>

Gaedtke, H.; Troe, J.

doi:10.1002/bbpc.19750790212

Cited by 47 publications

(10 citation statements)

References 54 publications

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“…17,18 The NO state distributions, despite severe fluctuations, can be described on average using statistical theories, implying dissociation on a barrierless PES. 14,19,20 Rate measurements 21,22 and theoretical calculations 15,16,23,24 have led to the same conclusion.…”

Section: Introductionmentioning

confidence: 57%

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Dem'yanenko

Dribinski

Reisler

et al. 1999

The Journal of Chemical Physics

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Angular distributions of state-selected NO and O products in the photoinitiated unimolecular decomposition of jet-cooled NO 2 have been measured by using both the photofragment ion imaging technique with velocity map imaging and ion time-of-flight translational spectroscopy. The recoil anisotropy parameter of the photofragments, ␤, depends strongly on the rotational angular momentum of the photoproduct. O( 3 P jϭ2,0 ) angular distributions are recorded at photolysis wavelengths 371.7, 354.7, and 338.9 nm. At these wavelengths, respectively, vibrational levels v ϭ0, vϭ0,1 and vϭ0 -2 of NO are generated. In addition, ␤ values for NO(vϭ2) in specific high rotational levels are determined at ϳ338 nm. The experimental observations are rationalized with a classical model that takes into account the transverse recoil component mandated by angular momentum conservation. The model is general and applicable in cases where fragment angular momentum is large, i.e., a classical treatment is justified. It is applied here both to the experimental NO 2 results, and results of quantum calculations of the vibrational predissociation of the Ne-ICl van der Waals complex. It is concluded that deviations from the limiting ␤ values should be prominent in fast, barrierless unimolecular decomposition, and in certain dissociation processes where a large fraction of the available energy is deposited in rotational excitation of the diatom. The application of the model to NO 2 dissociation suggests that the nuclear dynamics leading to dissociation involves a decrease in bending angle at short internuclear separations followed by a stretching motion. This interpretation is in accord with recent theoretical calculations.

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Section: Introductionmentioning

confidence: 57%

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Dem'yanenko

Dribinski

Reisler

et al. 1999

The Journal of Chemical Physics

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“…Further reactions, forming O 3 and N 2 O 5 , with increasing pressure also enter Φ tot [5]. In search of other possible reasons for quantum yield reductions, it appeared necessary to reinspect the influence of these reactions.…”

Section: Reanalysis Of Secondary Reactionsmentioning

confidence: 99%

“…This effect in part is explained by the combined use of the photon energy and thermal rovibrational energy of the NO 2 molecules prior to excitation for breaking the OϪNO bond [10]. A semiquantitative master equation treatment of this mechanism has been presented in [5] and [12]. A semiquantitative master equation treatment of this mechanism has been presented in [5] and [12].…”

Section: Introductionmentioning

confidence: 99%

Are Primary Quantum Yields of NO2 Photolysis at λ ≤ 398 nm Smaller than Unity?

Troe¹

2000

Zeitschrift Für Physikalische Chemie

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Primary quantum yields Φ of NO2 photolysis at wavelengths λ Յ 398 nm and at bath gas pressures below 1 bar are analyzed. Stern-Volmer plots for collisional photolysis quenching, from experiments at pressures between 10 and 1000 bar, do not indicate a substantial reduction of the quantum yield below unity for pressures below 1 bar. The consequences of the recently discovered fluctuations of specific rate constants k(E) for NO2 dissociation on collisional photolysis quenching are analyzed. These effects can lead to a small reduction of Φ at pressures below 1 bar which, however, is also smaller than the reduction reported in some experiments. Reanalysis of these experiments shows instead that, apart from experimental artifacts, the influence of the secondary reactions O ϩ NO2 (ϩ M) → NO3 (ϩ M), NO3 ϩ NO → 2 NO2, and O ϩ NO2 → O2 ϩ NO was underestimated. As a consequence, all experimental evidence so far is in favour of a low pressure primary quantum yield which is unity over the complete wavelength range 300Ϫ 398 nm. This leads to a revised recommendation of quantum yields Φ for the range 300Ϫ 430 nm at 298 K and 248 K. A revision of the limiting low pressure rate constant at 298 K of the reaction O ϩ NO2 ϩ N2 → NO3 ϩ N2 of (1.6 Ϯ0.2) ϫ10 Ϫ31 [N2] cm 3 molecule Ϫ1 s Ϫ1 is also recommended (to be employed together with Fc ϭ 0.6 and a limiting high pressure value of 2.2ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 ).

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“…Recent interest in these data arises from the need to assess the extent of ozone generation via NO 2 photodecomposition within the troposphere, which depends strongly on the reacthe years that followed, a great many quantum yield measurements for NO 2 were made at these and other wavelengths[Norrish, 1929;Holmes and Daniels, 1934;Hall, 1953;Blacet et al, 1962;Pitts et al, 1964;Jones and Bayes, 1973b;Troe, 1969;Gaedtke et al, 1972;Gaedtke and Troe, 1975; Hippler et al, 1975;Harker et al, 1977; …”

mentioning

confidence: 99%

Primary quantum yields of NO₂ photodissociation

Gardner¹,

Sperry²,

Calvert³

1987

J. Geophys. Res.

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A large discrepancy exists among recent estimates of the primary quantum efficiencies (ϕ1) of nitrogen dioxide photodecomposition, NO2 + hν → NO + O(3P), in the wavelength range from 374 to 396 nm. To resolve this problem, quantum yields of formation of NO, O2, and NO2 loss have been measured for NO2 vapor at low pressures (0.13–0.30 torr) irradiated at selected wavelengths (334.1–404.3 nm) and temperatures (273–370 K). From these data, estimates of ϕ1 were derived which confirm the previous findings of Jones and Bayes (1973b): ϕ1 increases rapidly from near zero at 424 nm to near unity for excitation at λ < 394 nm. The temperature and wavelength dependences of ϕ1 appear to be in qualitative accord with the simple theory of Pitts et al. (1964) that the energy deficiency for photodissociation of NO2 excited at λ > 397.9 nm (λdiss) is made up in large part from the rotational and vibrational energy of the NO2 molecules. Recommended values for ϕ1 based upon a review of these data and estimates made over a period of 58 years, are given as a function of wavelength.

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Primary Processes in the Photolysis of NO₂

Cited by 47 publications

References 54 publications

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Are Primary Quantum Yields of NO2 Photolysis at λ ≤ 398 nm Smaller than Unity?

Primary quantum yields of NO₂ photodissociation

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Primary Processes in the Photolysis of NO2

Cited by 47 publications

References 54 publications

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Product quantum-state-dependent anisotropies in photoinitiated unimolecular decomposition

Are Primary Quantum Yields of NO2 Photolysis at λ ≤ 398 nm Smaller than Unity?

Primary quantum yields of NO2 photodissociation

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Primary Processes in the Photolysis of NO₂

Primary quantum yields of NO₂ photodissociation