Journal ArticleDOI
Theoretical Study of the CH3NO2 Unimolecular Decomposition Potential Energy Surface
TLDR
In this paper, the complex potential energy surface for the unimolecular isomerization and dissociation of nitromethane (CH3NO2) was investigated theoretically at the G2MP2/B3LYP/6-311++G(2d,2p) level of theory.Abstract:
The complex potential energy surface for the unimolecular isomerization and dissociation of nitromethane (CH3NO2), including 10 CH3NO2 isomers, 46 interconversion transition states, and 16 major dissociation products, is probed theoretically at the G2MP2//B3LYP/6-311++G(2d,2p) level of theory. The geometries and relative energies for various stationary points are determined and are in good agreement with the available experimental values. Based on the calculated G2MP2 potential energy surface, the possible nitromethane unimolecular decomposition mechanism is discussed. It is shown that the most feasible decomposition channels for CH3NO2 are those that lead to 2CH3 + 2NO2, 2CH3O + 2NO, H2CO + HNO, and HCNO + H2O, respectively. Among them, 2CH3 and 2NO2 are produced by the direct C−N bond rupture of nitromethane, while the formation of the latter three products is initiated by CH3NO2 rearranging first to methyl nitrite or to aci-nitromethane. The C−N bond dissociation energy for nitromethane is calculated t...read more
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NOx Reduction from Diesel Emissions over a Nontransition Metal Zeolite Catalyst: A Mechanistic Study Using FTIR Spectroscopy
TL;DR: In this paper, the reaction of NO2 with acetaldehyde starts with the formation of acetate ions and subsequently the aci-anion of nitromethane, which is stabilized in the ionic environment of the zeolite to form a proposed O2NCH2NO2- intermediate.
Journal ArticleDOI
Nitrated lipids decompose to nitric oxide and lipid radicals and cause vasorelaxation.
Emersom Silva Lima,Marcelo G. Bonini,Ohara Augusto,Hermes Vieira Barbeiro,Heraldo Possolo de Souza,Dulcinéia Saes Parra Abdalla +5 more
TL;DR: In this article, the authors confirmed and extended previous studies by demonstrating that nitrolinoleate, chlolesteryl n-germinate, and nitrohydroxylinoleate induce vasorelaxation in a concentration-dependent manner while releasing nitric oxide that was characterized by chemiluminescence and EPR-based methodologies.
Journal ArticleDOI
Density-dependent liquid nitromethane decomposition: molecular dynamics simulations based on ReaxFF.
Naomi Rom,Sergey V. Zybin,Adri C. T. van Duin,William A. Goddard,Yehuda Zeiri,Gil Katz,Ronnie Kosloff +6 more
TL;DR: Atomic averaged local diffusion coefficients are shown to be sensitive to the reactions dynamics, and can be used to distinguish between time periods where chemical reactions occur and diffusion-dominated, nonreactive time periods.
Journal ArticleDOI
Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane
TL;DR: The derivation and implementation of analytical gradients for FNO-CC are reported, including all orbital relaxation for both noncanonical and semicanonical perturbed orbitals, and several new orbital relaxation contributions to the CC density matrices are introduced.
Journal ArticleDOI
Enhanced Thermal Decomposition of Nitromethane on Functionalized Graphene Sheets: Ab Initio Molecular Dynamics Simulations
TL;DR: Ab initio molecular dynamics simulations showing that carbon vacancy defects within the plane of the FGSs, functionalized with oxygen-containing groups, greatly accelerate the thermal decomposition of NM and its derivatives are reported.
References
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Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate
TL;DR: In this paper, the photodissociation rate coefficients and photodynamic lifetimes for nitromethane, methyl nitrite, and methyl nitrate were calculated as a function of altitude from their measured visible and near ultraviolet photoabsorption cross sections at 298 K.