Approach to the Atmospheric Chemistry of Methyl Nitrate and Methylperoxy Nitrite. Chemical Mechanisms of Their Formation and Decomposition Reactions in the Gas Phase

Arenas, Juan F.; Ávila, Francisco; Otero, Juan C.; Peláez, Daniel; Soto, Juan

doi:10.1021/jp075546n

Cited by 41 publications

(35 citation statements)

References 44 publications

(40 reference statements)

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“…The present study not only entirely reproduced the reported isomeric‐conversion and DCs around HOCH 2 NO 2 but also disclosed many other conformers and reaction channels at the levels of B3LYP/6‐31G(d) and B3LYP/6‐311++G(d,p). Related to the chemistry of the atmosphere, many studies were made for methyl nitrate 21 and methylperoxy nitrite 31 , but the isomeric forms and isomerization channels reported were essentially the same as the present study, although some DCs not treated in the present study were shown for radical‐pair processes . A similar result to this study was reported for an isomerization channel between methyl nitrate 21 and methoxy dioxaziridine 45 in connection with the reaction of triplet nitrenes with oxygen .…”

Section: Remarks On the Present Approachsupporting

confidence: 83%

“…As for isomerization routes at high energy regions, rigorous treatments need to be made for deeper understanding. Radical‐pair channels including CH 3 O + NO 2 have been studied in connection with methyl nitrate 21 and methyl peroxynitrite 31 . In some special cases, multi‐reference treatments as well as excited‐surface treatments including conical intersections and seams should also be taken into account.…”

Section: Remarks On the Present Approachmentioning

confidence: 99%

“…This article describes a study on the exploration of isomers, isomerization reactions, as well as their reaction routes for H 3 CNO 3 using SHS‐ADDF. Studies on H 3 CNO 3 were reported recently in relation to combustion and atmospheric chemistry . The reaction channels for some isomers of H 3 CNO 3 including nitromethanol (HOCH 2 NO 2 ) and nitrosooxymethnol (HOCH 2 ONO) were elucidated using hybrid density‐functional‐theory (DFT) B3LYP method in connection with radical‐molecule reaction of CH 2 OH with NO 2 .…”

Section: Introductionmentioning

confidence: 99%

“…The reaction channels for some isomers of H 3 CNO 3 including nitromethanol (HOCH 2 NO 2 ) and nitrosooxymethnol (HOCH 2 ONO) were elucidated using hybrid density‐functional‐theory (DFT) B3LYP method in connection with radical‐molecule reaction of CH 2 OH with NO 2 . The reaction channels involving methyl nitrate (H 3 CONO 2 ) and methyl peroxynitrite (H 3 COONO) related to atmospheric systems were studied in different levels of calculations . We assumed that interesting chemistry would be discovered more from the GRRM for H 3 CNO 3 because of its potential of the formation of various functional groups, including OH, OO, OOH, OOO, CO, CHO, COOH, COOOH, CN, NH, NH 2 , NO, NO 2 , NO 3 , NOO, ONO, NOH, NOOH, NHOH, CH, CH 2 , and CH 3 , which can compose various chemical structures.…”

Section: Introductionmentioning

confidence: 99%

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Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

et al. 2017

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Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface (PES) is performed for H CNO using the Scaled Hypersphere Search-Anharmonic Downward Distortion Following (SHS-ADDF) method. The molecular formula of H CNO includes functional groups of CH , OH, NH , COOH, NO, NO , and NO , which are very important in connection with amino acids and NOx. Geometrical structures and interconversion pathways are disclosed after 18719781 force calculations and 534726 Hessian calculations at the level of B3LYP/6-31G(d). The explored results are confirmed to be valid, especially for the important lower energy regions, by re-optimization at the higher level of B3LYP/6-311++G(d,p). A global reaction route-mapping using SHS-ADDF demonstrates the entire view and undeveloped landscapes on PES of H CNO . Typical compounds of H CNO , aminoxy formic acid, hydroxycarbamic acid, aminoperformic acid, hydroxymethyl nitrite, nitromethanol, methyl nitrate, methyl peroxynitrite, and dioxaziridine, are well separated from others by very high energy-barriers. The stable-most conformer of H CNO is difficult to be determined, because of seven structures existing with nearly the same energies within 5.7 kJ/mol at the level of CCSD(T)/aug-cc-pVTZ. © 2017 Wiley Periodicals, Inc.

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Section: Remarks On the Present Approachsupporting

confidence: 83%

Section: Remarks On the Present Approachmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

et al. 2017

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“…There have been several theoretical investigations of the energetics and mechanisms of (R1a) and (R1b) . A composite of these energetics is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Pressure Dependence and Kinetic Isotope Effects in the Absolute Rate Constant for Methoxy Radical Reacting with NO₂

Chai

Dibble

2014

Int J of Chemical Kinetics

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We have investigated the kinetics for the reaction CH3O• + NO2 in N2 bath gas. The rate constants are well‐fit by the Troe expression over the temperature (250–335 K) and pressure range (30–700 Torr) investigated. The termolecular rate constant is given by italick1normala0=4.29−0.37+0.40×10−29()italicT/298−1.65±1.11 cm6 molecule−2 s−1, and the rate constant at the high‐pressure limit is given by italick1normala∞=1.95±0.03×10−11()italicT/298−1.13±0.18 cm3 molecule−1 s−1. We also studied the kinetics of the reaction of CD3O• + NO2 as a function of temperature and pressure under similar conditions as those for CH3O• + NO2. The resulting low‐ and high‐pressure limiting rate constants are italick2normala0=9.97−0.91+1.00×10−29()italicT/298−4.79±0.92 cm6 molecule−2 s−1 and italick2normala∞=1.91±0.02×10−11()italicT/298−1.11±0.09 cm3 molecule−1 s−1, respectively. The rate constants for the two isotopologues track each other closely as the high‐pressure limit is approached. The present results agree with most previous results at 295 K over a range of pressures, but there is substantial disagreement about the temperature dependence.

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Computational Treatments of Peroxy Radicals in Combustion and Atmospheric Reactions

Kuwata¹

2014

Patai's Chemistry of Functional Groups

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I. INTRODUCTIONPeroxy species are key intermediates in chemical reactions in both combustion 1, 2 and the troposphere 3,4 , which is the layer of the atmosphere extending from the Earth's surface to roughly 15 km in altitude, where temperature stops decreasing with altitude 5 . As is true for the study of reactive intermediates in general, advances in the understanding of peroxides have come from a dialog between theory-both electronic structure and statistical rate theory calculations-and experiment. This chapter focuses on the insights that electronic structure calculations, particularly those involving composite methods and density functional theory (DFT), have brought to peroxide chemistry. As much as possible, experimental results will be cited to validate or challenge the predictions of electronic structure theory. (While a direct comparison between electronic structure predictions and experimental data sometimes requires applications of statistical rate theory and other 1

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Approach to the Atmospheric Chemistry of Methyl Nitrate and Methylperoxy Nitrite. Chemical Mechanisms of Their Formation and Decomposition Reactions in the Gas Phase

Cited by 41 publications

References 44 publications

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

Pressure Dependence and Kinetic Isotope Effects in the Absolute Rate Constant for Methoxy Radical Reacting with NO₂

Computational Treatments of Peroxy Radicals in Combustion and Atmospheric Reactions

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Approach to the Atmospheric Chemistry of Methyl Nitrate and Methylperoxy Nitrite. Chemical Mechanisms of Their Formation and Decomposition Reactions in the Gas Phase

Cited by 41 publications

References 44 publications

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H3CNO3

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H3CNO3

Pressure Dependence and Kinetic Isotope Effects in the Absolute Rate Constant for Methoxy Radical Reacting with NO2

Computational Treatments of Peroxy Radicals in Combustion and Atmospheric Reactions

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Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H₃CNO₃

Pressure Dependence and Kinetic Isotope Effects in the Absolute Rate Constant for Methoxy Radical Reacting with NO₂