Photochemistry of Molecules Relevant to the Atmosphere: Photodissociation of Nitric Acid in the Gas Phase

Huber, J. Robert

doi:10.1002/cphc.200400071

Cited by 16 publications

(22 citation statements)

References 43 publications

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“…about the single N-O bond [2,5]. For the S 1 state the energy difference of the two optimized geometries was found to be 15.6 kcal/mol with the pyramidal structure being the lower.…”

Section: Resultsmentioning

confidence: 90%

“…The photochemical decay of nitric acid HNO 3 in the gas phase has been well investigated motivated mainly by the importance of this molecule for atmospheric chemistry [1][2]. Just recently the first global distributions of nitric acid in the troposphere and the stratosphere have been reported employing infrared satellite measurements [3].…”

Section: Introductionmentioning

confidence: 99%

“…The various photodissociation pathways emerging from this excitation process are summarised in the following scheme [2]:…”

Section: Introductionmentioning

confidence: 99%

“…This clear preference of the breaking of the strong -N=O bond (~ 500 kJ/mol) over that of the much weaker -N-O bond (~200 kJ/mol) at higher excitation energy is somewhat surprising and let to speculations about the mechanistic features of this branching process [2].…”

Section: Introductionmentioning

confidence: 99%

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An ab initio and dynamics study of the photodissociation of nitric acid HNO3

Nonella

Suter

Huber

2010

Chemical Physics Letters

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We investigated the photodissociation of HNO3 within the first (300 nm) and the third (200 nm) absorption band. The relevant S1 and S3 potential energy surfaces were calculated by taking into account the N-O single bond and N=O "double" bond distances. The striking feature of the dynamical analysis is a bifurcation of the wave packet on the S3 surface which explains the branching into the two reaction pathways with the products OH+NO2 and O+HONO found in experiments. Dissociation on the S1 surface is predicted to proceed along a single channel leading to OH+NO2, both in their electronic ground states. Corresponding author: We investigated the photodissociation of HNO 3 within the first (300 nm) and the third (200 nm) absorption band. The relevant S 1 and S 3 potential energy surfaces were calculated by taking into account the N-O single bond and N=O "double" bond distances. The striking feature of the dynamical analysis is a bifurcation of the wave packet on the S 3 surface which explains the branching into the two reaction pathways with the products OH+NO 2 and O+HONO found in experiments. Dissociation on the S 1 surface is predicted to proceed along a single channel leading to OH+NO 2 , both in their electronic ground states.

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“…about the single N-O bond [2,5]. For the S 1 state the energy difference of the two optimized geometries was found to be 15.6 kcal/mol with the pyramidal structure being the lower.…”

Section: Resultsmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

“…The various photodissociation pathways emerging from this excitation process are summarised in the following scheme [2]:…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

An ab initio and dynamics study of the photodissociation of nitric acid HNO3

Nonella

Suter

Huber

2010

Chemical Physics Letters

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“…75 NO 3 . radicals undergo rapid photo-dissociation during the day, 76 so that they are most important as atmospheric oxidants at night. Observations at several forested sites have led to the suggestion that oxidation by NO 3 .…”

Section: Gas Phase Oxidation Of Bvocsmentioning

confidence: 99%

Reactions of Biogenic Volatile Organic Compounds in the Atmosphere

Monson

2010

The Chemistry and Biology of Volatiles

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Potential sources of nitrous acid (HONO) and their impacts on ozone: A WRF‐Chem study in a polluted subtropical region

et al. 2016

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Current chemical transport models commonly undersimulate the atmospheric concentration of nitrous acid (HONO), which plays an important role in atmospheric chemistry, due to the lack or inappropriate representations of some sources in the models. In the present study, we parameterized up-to-date HONO sources into a state-of-the-art three-dimensional chemical transport model (Weather Research and Forecasting model coupled with Chemistry: WRF-Chem). These sources included (1) heterogeneous reactions on ground surfaces with the photoenhanced effect on HONO production, (2) photoenhanced reactions on aerosol surfaces, (3) direct vehicle and vessel emissions, (4) potential conversion of NO 2 at the ocean surface, and (5) emissions from soil bacteria. The revised WRF-Chem was applied to explore the sources of the high HONO concentrations (0.45-2.71 ppb) observed at a suburban site located within complex land types (with artificial land covers, ocean, and forests) in Hong Kong. With the addition of these sources, the revised model substantially reproduced the observed HONO levels. The heterogeneous conversions of NO 2 on ground surfaces dominated HONO sources contributing about 42% to the observed HONO mixing ratios, with emissions from soil bacterial contributing around 29%, followed by the oceanic source (~9%), photochemical formation via NO and OH (~6%), conversion on aerosol surfaces (~3%), and traffic emissions (~2%). The results suggest that HONO sources in suburban areas could be more complex and diverse than those in urban or rural areas and that the bacterial and/or ocean processes need to be considered in HONO production in forested and/or coastal areas. Sensitivity tests showed that the simulated HONO was sensitive to the uptake coefficient of NO 2 on the surfaces. Incorporation of the aforementioned HONO sources significantly improved the simulations of ozone, resulting in increases of ground-level ozone concentrations by 6-12% over urban areas in Hong Kong and the Pearl River Delta region. This result highlights the importance of accurately representing HONO sources in simulations of secondary pollutants over polluted regions. ZHANG ET AL.MODELING HONO IN A SUBTROPICAL REGION 3645

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Photochemistry of Molecules Relevant to the Atmosphere: Photodissociation of Nitric Acid in the Gas Phase

Cited by 16 publications

References 43 publications

An ab initio and dynamics study of the photodissociation of nitric acid HNO3

An ab initio and dynamics study of the photodissociation of nitric acid HNO3

Reactions of Biogenic Volatile Organic Compounds in the Atmosphere

Potential sources of nitrous acid (HONO) and their impacts on ozone: A WRF‐Chem study in a polluted subtropical region

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