Searcharxiv⌕ Search
Home/Archive/arXiv

arXiv · 2408.17277

On the key kinetic interactions between NOx and unsaturated hydrocarbons: H-atom abstraction from C3-C7 alkynes and dienes by NO2

Zhengyan Guo·Hongqing Wu·Ruoyue Tang·Xinrui Ren·Ting Zhang·Mingrui Wang·Guojie Liang·Hengjie Guo·Song Cheng
View original source ↗Read source document ↗Export metadata ↓

Abstract

An adequate understanding of NOx interacting chemistry is a prerequisite for a smoother transition to carbon lean and carbon free fuels such as ammonia and hydrogen. In this regard, this study presents a comprehensive study on the H atom abstraction by NO2 from C3 to C7 alkynes and dienes forming 3 HNO2 isomers (i.e., TRANS HONO, HNO2, and CIS HONO), encompassing 8 hydrocarbons and 24 reactions. Through a combination of high level quantum chemistry computation, the rate coefficients for all studied reactions, over a temperature range from 298 to 2000 K, are computed based on Transition State Theory using the Master Equation System Solver program with considering unsymmetric tunneling corrections. Comprehensive analysis of branching ratios elucidates the diversity and similarities between different species, different HNO2 isomers, and different abstraction sites. Incorporating the calculated rate parameters into a recent chemistry model reveals the significant influences of this type of reaction on model performance, where the updated model is consistently more reactive for all the alkynes and dienes studied in predicting autoignition characteristics. Sensitivity and flux analyses are further conducted, through which the importance of H atom abstractions by NO2 is highlighted. With the updated rate parameters, the branching ratios in fuel consumption clearly shifts towards H atom abstractions by NO2 while away from H atom abstractions by OH. The obtained results emphasize the need for adequately representing these kinetics in new alkyne and diene chemistry models to be developed by using the rate parameters determined in this study, and call for future efforts to experimentally investigate NO2 blending effects on alkynes and dienes.

Explore related subjects

physics.chem-ph

Keep this discovery

BibTeXRIS

Zhengyan Guo, Hongqing Wu, Ruoyue Tang, Xinrui Ren, Ting Zhang, Mingrui Wang, Guojie Liang, Hengjie Guo, Song Cheng. 2024-08-30. On the key kinetic interactions between NOx and unsaturated hydrocarbons: H-atom abstraction from C3-C7 alkynes and dienes by NO2. https://arxiv.org/abs/2408.17277

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Breaking Water at Graphene Defects

Water dissociation at solid surfaces underpins processes ranging from corrosion and catalysis to electrochemistry and photovoltaics. Defects often serve as reactive sites for dissociation, yet how solvation influences water dissociation at such sites remains poorly understood. Here, we use state-of-the-art machine-learned interatomic potentials to explore water dissociation at defective graphene-water interfaces. We show that solvation qualitatively changes the reaction mechanism at a graphene single vacancy (SV), opening pathways that are absent for an isolated water molecule. Whereas the gas-phase process proceeds via a single concerted channel, the solvated SV splits water through two competing pathways: a basic route forming SV-H and OH-(aq), and an acidic route forming SV-OH and H3O+(aq). These lower-barrier pathways produce distinct chemisorbed intermediates that enhance graphene-water adsorption. Accordingly, even a simple carbon vacancy gives rise to unexpectedly rich interfacial chemistry, coupling surface chemistry to interfacial charge and wettability, with implications for carbon functionalization and nanofluidic transport.

physics.chem-ph↗
arXiv2026

Comprehensive Study of L-Menthol and Octanoic Acid as a Hydrophobic Eutectic Solvent

Hydrophobic eutectic solvents (HES) based on natural compounds represent promising green alternatives to conventional solvents. In this work, we investigate the physicochemical, structural, and dynamical properties of an ES formed by L-menthol and octanoic acid using a combined experimental and molecular dynamics simulation approach. Five compositions with molar ratios from 1:3 to 3:1 were studied with molecular dynamics simulation in the temperature range 15 degrees C to 35 degrees C. Experimental measurements of density and viscosity in the temperature range from 5 degrees C to 35 degrees C were complemented with results obtained from MD simulations employing the OPLS force field. Structural analyses based on radial distribution functions and Kirkwood-Buff integrals reveal that the dominant interactions in the mixture are hydrogen bonds between L-menthol and octanoic acid molecules. Dynamic properties, including self-diffusion coefficients and hydrogen-bond lifetimes, indicate that intermolecular hydrogen bonds between the two components are stronger and longer-lived than bonds between identical species. These findings provide molecular-level insight into the structure and transport properties of menthol-based ESs relevant for green solvent applications.

physics.chem-ph↗
arXiv2026

More is not always better: Dissociative photoionization limits the EUV absorbing photacid generator pentafluorophenyl triflate in photolithography

Pentafluorophenyl triflate has been explored as a highly absorbing neutral photoacid generator (PAG) candidate for next generation chemically amplified resists used in extreme ultraviolet (EUV) lithography. Although increased fluorination enhances EUV absorption, this study demonstrates that such an approach does not necessarily improve photoacid generation efficiency. Using photoelectron-photoion coincidence (PEPICO) spectroscopy at the 92 eV photon energy of the EUV scanners in combination with quantum chemical calculations, the dissociative photoionization of pentafluorophenyl triflate was systematically investigated. The photoionization mass spectrum reveals extensive fragmentation, with the parent ion contributing only 3.1 % of the total signal and CF$_3^+$ representing the dominant product ion. Computed appearance energies align well with experimental trends and support a sequential fragmentation pathway involving loss of SO$_2$, CF$_3$, and CO. Crucially, none of the major dissociation channels yield precursors capable of forming triflic acid, the strong photoacid required for efficient deprotection reactions in chemically amplified resists. Combined with previous dissociative electron attachment studies indicating similarly unfavorable fragmentation, the results demonstrate that despite its high EUV absorption cross section, pentafluorophenyl triflate is unsuitable as a PAG for EUV lithography. The findings highlight the importance of understanding fundamental photoionization and electron interaction mechanisms to guide the rational design of next generation high performance EUV photoresists.

physics.chem-ph↗