Ab Initio Molecular Orbital Calculations on NO+·(H2O)n Cluster Ions. Part I:  Minimum-Energy Structures and Possible Routes to Nitrous Acid Formation

Hammam, Essam; Lee, E. P. F.; Dyke, John M.

doi:10.1021/jp994278t

Cited by 21 publications

(37 citation statements)

References 17 publications

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“…For each of these, there are several structures very close in energy with different orientations of the hydrogen atoms of the water molecules. The MP2 calculations are consistent with previous work [20] where structure 2a has the lowest energy. When zero point energy (ZPE) is taken into account, the energy difference is approximately 10 kJ mol −1 .…”

Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andsupporting

confidence: 90%

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Linton¹,

Wright²,

Besley³

2018

Phil. Trans. R. Soc. A.

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Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO(HO) clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO(HO) that is too high and incorrectly predict the lowest energy structure of NO(HO), and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO Ab initio molecular dynamics (AIMD) simulations were performed to study the NO(HO) [Formula: see text] H(HO) + HONO reaction to investigate the formation of HONO from NO(HO) Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO(HO) complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'.

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Section: Density Functional Theory and Mp2 Studies Of No + H 2 O Andsupporting

confidence: 90%

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Linton¹,

Wright²,

Besley³

2018

Phil. Trans. R. Soc. A.

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“…Koel and coworkers [148][149][150]152 proposed that this isomerization occurs via the free O-H groups on amorphous ice, and it is possible that a similar process occurs in the thin films studied here. Once formed, the asymmetric ONONO 2 Experimental and theoretical studies [153][154][155] of the reactions of gas phase clusters of hydrated NO + show that reaction to generate HONO occurs with four or more water molecules bound to NO + . Bands due to the asymmetric ONONO 2 have not yet been identified on silica surfaces at room temperature.…”

Section: Mechanisms and Modelsmentioning

confidence: 99%

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Finlayson-Pitts

Wingen

Sumner

et al. 2002

Phys. Chem. Chem. Phys.

600

767

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The heterogeneous reaction of NO 2 with water on the surface of laboratory systems has been known for decades to generate HONO, a major source of OH that drives the formation of ozone and other air pollutants in urban areas and possibly in snowpacks. Previous studies have shown that the reaction is first order in NO 2 and in water vapor, and the formation of a complex between NO 2 and water at the air-water interface has been hypothesized as being the key step in the mechanism. We report data from long path FTIR studies in borosilicate glass reaction chambers of the loss of gaseous NO 2 and the formation of the products HONO, NO and N 2 O. Further FTIR studies were carried out to measure species generated on the surface during the reaction, including HNO 3 , N 2 O 4 and NO 2 + . We propose a new reaction mechanism in which we hypothesize that the symmetric form of the NO 2 dimer, N 2 O 4 , is taken up on the surface and isomerizes to the asymmetric form, ONONO 2 . The latter autoionizes to NO + NO 3 À , and it is this intermediate that reacts with water to generate HONO and surface-adsorbed HNO 3 . Nitric oxide is then generated by secondary reactions of HONO on the highly acidic surface. This new mechanism is discussed in the context of our experimental data and those of previous studies, as well as the chemistry of such intermediates as NO + and NO 2 + that is known to occur in solution. Implications for the formation of HONO both outdoors and indoors in real and simulated polluted atmospheres, as well as on airborne particles and in snowpacks, are discussed. A key aspect of this chemistry is that in the atmospheric boundary layer where human exposure occurs and many measurements of HONO and related atmospheric constituents such as ozone are made, a major substrate for this heterogeneous chemistry is the surface of buildings, roads, soils, vegetation and other materials. This area of reactions in thin films on surfaces (SURFACE ¼ Surfaces, Urban and Remote: Films As a Chemical Environment) has received relatively little attention compared to reactions in the gas and liquid phases, but in fact may be quite important in the chemistry of the boundary layer in urban areas.

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“…Millions of dollars were spent to prove an acceptable safety profi le of the water-soluble forms of the compound, such as artesunate and artelinate, over the lipid-soluble forms such as artemether or arteether ( 4). Finally, in 2004, a regulatory dossier was fi led with the U.S. Food and Drug Adminstration (FDA) and artesunate was made available to treat severe and complicated malaria in the United States ( 5). Just last year, the FDA approved an oral artemisinin combined therapy for less severe cases.…”

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confidence: 99%

Ion Chemistry Mediated by Water Networks

Siefermann

Abel

2010

Science

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Ab Initio Molecular Orbital Calculations on NO⁺·(H₂O)_n Cluster Ions. Part I: Minimum-Energy Structures and Possible Routes to Nitrous Acid Formation

Cited by 21 publications

References 17 publications

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Ion Chemistry Mediated by Water Networks

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Ab Initio Molecular Orbital Calculations on NO+·(H2O)n Cluster Ions. Part I: Minimum-Energy Structures and Possible Routes to Nitrous Acid Formation

Cited by 21 publications

References 17 publications

Quantum chemical study of the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO + .(H 2 O) n =1−5 clusters

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Ion Chemistry Mediated by Water Networks

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Product

Resources

About

Ab Initio Molecular Orbital Calculations on NO⁺·(H₂O)_n Cluster Ions. Part I: Minimum-Energy Structures and Possible Routes to Nitrous Acid Formation

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters

Quantum chemical study of the structure, spectroscopy and reactivity of NO ⁺ .(H ₂ O) _{n
=1−5} clusters