Reaction of OH + NO2 + M: Kinetic evidence of isomer formation

Hippler, H.; Nasterlack, Steffen; Striebel, Frank

doi:10.1039/b201932a

Cited by 73 publications

(184 citation statements)

References 31 publications

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“…At very high temperatures and pressures the HOONO dissociation lifetime is much shorter. This has been observed in the form of bi-exponential OH decays by Hippler et al and D'Ottone et al (S8,S30,S31) These decays were fit to extract the rate constants k1a and k1b as well as the equilibrium constant K 1b . Hippler et al measured k 1b /k 1a = 0.15 at 430 K and 3750 Torr He, with a HOONO dissociation rate of 20 µs (S31).…”

Section: Discussion Of the Hoono/hono 2 Branching Ratiomentioning

confidence: 99%

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Mollner

Valluvadasan

Feng

et al. 2010

Science

128

169

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Honing in on HONO 2 Modeling air pollution requires knowledge of all the interrelated reactions occurring in the atmosphere. Among the most significant is the formation of nitric acid (HONO 2 ) from OH and NO 2 radicals. One sticking point in the study of this reaction has been the uncertainty in how often radicals link through an O-O rather than an O-N bond. Mollner et al. (p. 646 ) measured the partitioning coefficient, as well as the overall consumption rate of the radicals, with an array of highly sensitive spectroscopic techniques in the laboratory. The measurements yielded a well-defined rate constant for nitric acid formation, which was applied to the prediction of ozone levels in atmospheric simulations of the Los Angeles basin.

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Section: Discussion Of the Hoono/hono 2 Branching Ratiomentioning

confidence: 99%

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Mollner

Valluvadasan

Feng

et al. 2010

Science

128

169

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“…2 reaction, with structures of trans-perp and cis-cis HOONO shown. HOONO energy levels are from present work; HONO 2 energy relative to cis-cis HOONO are from Bean et al 9 and OHϩNO 2 energy relative to cis-cis HOONO is from Hippler, Nasterlack, and Striebel 3 and Dixon et al 10 Pathways for direct isomerization from HOONO into HONO 2 are not shown because they have substantially higher barriers compared to dissociation into OH and NO 2 .…”

Section: Introductionmentioning

confidence: 99%

“…At some conditions, these experiments measured the total reaction rate coefficient, k 1 ϭk 1a ϩk 1b , while assuming the observed decay was due only to k 1a . Recent measurements 3,9,11 have found that HOONO is indeed formed in reaction ͑1͒ with a measurable yield of k 1b /(k 1a ϩk 1b )Ϸ5 -10% at low pressures ͑27 hPa͒ and room temperature. Thus, to the extent that HOONO is formed, the total rate of reaction ͑1͒ overestimates the net loss of HO x and NO x to HNO 3 .…”

Section: Introductionmentioning

confidence: 99%

“…The rate constant of this reaction has been the topic of some controversy [1][2][3][4][5][6][7] because the high and low pressure rate constants could not be reconciled with a single termolecular rate expression. This discrepancy can be resolved by the inclusion of a second minor channel forming a more weakly bound isomer of nitric acid, peroxynitrous acid, or HOONO, as first predicted by Robertshaw and Smith: 8 OHϩNO 2 ϩM →HONO 2 ϩM ͑1a͒…”

Section: Introductionmentioning

confidence: 99%

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Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

Fry

Nizkorodov

Okumura

et al. 2004

The Journal of Chemical Physics

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The weakly bound HOONO product of the OHϩNO 2 ϩM reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2 1 ). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2 1 band is observed under thermal ͑223-238 K͒ conditions at 6971 cm Ϫ1 . We assign the previously published ͑warmer temperature͒ HOONO spectrum to the 2 1 band at 6365 cm Ϫ1 and 2 1 -containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm Ϫ1 is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa ͑in a buffer gas of predominantly Ar͒. The temperature dependence of the trans-perp HOONO lifetime in the range 223-238 K yields an isomerization barrier of 33Ϯ12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples ͓CCSD͑T͔͒ model, using a correlation consistent polarized triple basis set ͑cc-pVTZ͒. The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level ͓CCSD͑T͒/ cc-pVTZ͔ and with a quadruple basis set using the structure determined at the triple basis set ͓CCSD͑T͒/cc-pVQZ//CCSD͑T͒/cc-pVTZ͔. These calculations predict that the anti form of perp-perp HOONO has an energy of ⌬E 0 ϭ42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of ⌬H 298 ‡0 ϭ41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO 2 is also calculated as a function of photon excitation energy in the range 3500-7500 cm Ϫ1 , assuming D 0 ϭ83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193-273 K. Semiempirical calculations of the oscillator strengths for 2 1 (cis-cis HOONO) and 2 1 (trans-perp HOONO) are performed using ͑1͒ a one-dimensional anharmonic model and ͑2͒ a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory ͑B3LYP͒,...

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“…An intensive investigation of discrepancies between low-and high-pressure values of the rate led several groups to propose that a secondary channel OHϩNO 2 ϩM →HOONOϩM competes with the primary reaction channel at higher total pressures. [1][2][3][4][5][6][7] Despite the kinetics evidence, detection of gasphase HOONO eluded several concentrated detection efforts 2,4,5 and its production as a stable species in the OH ϩNO 2 ϩM reaction remained controversial until very recently.…”

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confidence: 99%

Rotational spectrum of cis–cis HOONO

Drouin

Fry

Miller

2004

The Journal of Chemical Physics

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The pure rotational spectrum of cis-cis peroxynitrous acid, HOONO, has been observed. Over 220 transitions, sampling states up to JЈϭ67 and K a Јϭ31, have been fitted with an rms uncertainty of 48.4 kHz. The experimentally determined rotational constants agree well with ab initio values for the cis-cis conformer, a five-membered ring formed by intramolecular hydrogen bonding. The small, positive inertial defect ⌬ϭ0.075667(60) amu Å 2 and lack of any observable torsional splittings in the spectrum indicate that cis-cis HOONO exists in a well-defined planar structure at room temperature.

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Reaction of OH + NO2 + M: Kinetic evidence of isomer formation

Cited by 73 publications

References 31 publications

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

Rotational spectrum of cis–cis HOONO

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