4.6 Article

Unimolecular Reactions of 2,4-Dimethyloxetanyl Radicals

Related references

Note: Only part of the references are listed.
Article Chemistry, Physical

Automated Reaction Kinetics of Gas-Phase Organic Species over Multiwell Potential Energy Surfaces

Judit Zador et al.

Summary: Automation of rate-coefficient calculations for gas-phase organic species has revolutionized the computational exploration of these complex systems by providing rigor, speed, and removing manual labor and associated errors. This paper provides an overview of this rapidly evolving field and showcases the capabilities of our own automated tool, KinBot, through five detailed examples. The examples focus on combustion and atmospheric chemistry of species containing C, H, O, and N atoms, which are relevant to molecular weight growth and autoxidation processes. They demonstrate the power of automation and identify challenges for future research.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

Article Thermodynamics

Probing O2 dependence of hydroperoxy-butyl reactions via isomer-resolved speciation

Samuel W. Hartness et al.

Summary: The degenerate chain-branching mechanisms of n-alkanes involve the formation of hydroperoxy-alkyl radicals ((Q)Over dotOOH) through (R)Over dot + O-2 reactions, leading to a competition between unimolecular decomposition and second-O-2-addition. The quantitative measurements of partially oxidized intermediates formed from (Q)Over dotOOH reactions provide critical constraints for accurate modeling of combustion chemistry. The influence of temperature and oxygen concentration on intermediates from the unimolecular decomposition of (Q)Over dotOOH was examined, and the O-2-dependence of species profiles was quantified.

PROCEEDINGS OF THE COMBUSTION INSTITUTE (2023)

Article Thermodynamics

Probing O 2-dependence of tetrahydrofuranyl reactions via isomer-resolved speciation

Alanna L. Koritzke et al.

Summary: This study investigates the formation of intermediates in the low-temperature oxidation of tetrahydrofuran and the influence of temperature and oxygen concentration on this process. The results show that the formation of most species is dependent on the oxygen concentration and the current chemical kinetics mechanisms cannot accurately describe this dependence.

COMBUSTION AND FLAME (2023)

Article Engineering, Chemical

Characterization of the low-temperature oxidation chemistry of an unsaturated aldehyde 2-butenal in a Jet-stirred reactor

Zhongkai Liu et al.

PROCEEDINGS OF THE COMBUSTION INSTITUTE (2022)

Review Thermodynamics

Chemical kinetics of cyclic ethers in combustion

Luc-Sy Tran et al.

Summary: This article systematically analyzes the gas-phase oxidation chemistry of Cyclic Ethers (CEs) using both experimental and theoretical methods. It gives an overview of the significance of CEs as intermediates during alkane low-temperature oxidation and discusses their potential as biofuels derived from lignocellulosic biomass. The article also reviews the different theoretical and experimental methods used to study the electronic structure, thermochemical and kinetic data, formation, and degradation of CEs. Future research directions are proposed as well.

PROGRESS IN ENERGY AND COMBUSTION SCIENCE (2022)

Article Chemistry, Physical

Stereoisomer-dependent unimolecular kinetics of 2,4-dimethyloxetanyl peroxy radicals

Anna C. Doner et al.

Summary: In this study, the pressure- and temperature-dependent kinetics of the peroxy radicals derived from 2,4-dimethyloxetane were investigated. The reactivity of diastereomeric cyclic ether peroxy radicals was found to be significantly different, and ring-opening reactions produced unique products that connected with species in other chemical kinetics mechanisms through cross-over reactions. The results of this study are crucial for the development of detailed sub-mechanisms for cyclic ether intermediates and provide insights into the effects of stereoisomers on reaction pathways and product yields.

FARADAY DISCUSSIONS (2022)

Article Chemistry, Physical

Isomer-dependent reaction mechanisms of cyclic ether intermediates:cis-2,3-dimethyloxirane andtrans-2,3-dimethyloxirane

Anna C. Doner et al.

Summary: The study examines the isomer dependence of 2,3-dimethyloxirane reaction mechanisms to minimize mechanism truncation error. The results reveal complex consumption pathways for cyclic ethers, necessitating the expansion of submechanisms in chemical kinetics mechanisms.

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS (2021)

Article Chemistry, Physical

Thermal Decomposition of 2-Methyltetrahydrofuran behind Reflected Shock Waves over the Temperature Range of 1179-1361 K

Balla Rajakumar et al.

Summary: The thermal decomposition of 2-methyltetrahydrofuran (2-MTHF) was studied using reflected shock waves, identifying methane, ethylene, ethane, 1,3-butadiene, propylene, acetaldehyde, and acetylene as the main decomposition products. The experimentally determined rate coefficients followed an Arrhenius expression, and quantum chemistry methods were used to calculate energetics and kinetics of various dissociation pathways. The study found that initial decomposition of 2-MTHF occurs primarily through ring-methyl single bond fission, with temperature-dependent rate coefficients calculated using RRKM theory.

JOURNAL OF PHYSICAL CHEMISTRY A (2021)

Review Thermodynamics

Influence of functional groups on low-temperature combustion chemistry of biofuels

Brandon Rotavera et al.

Summary: Ongoing progress in synthetic biology, metabolic engineering, and catalysis has led to the production of diverse advanced biofuels. Understanding the connections between molecular structure and ignition at low temperatures remains a key priority addressed through chemical kinetics modeling. The review highlights the importance of functional groups in influencing chain reactions and the need for further research to address fundamental questions in biofuel ignition.

PROGRESS IN ENERGY AND COMBUSTION SCIENCE (2021)

Article Multidisciplinary Sciences

Watching a hydroperoxyalkyl radical (•QOOH) dissociate

Anne S. Hansen et al.

Summary: The prototypical hydroperoxyalkyl radical (center dot QOOH) intermediate, formed transiently in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay. Direct time-domain measurements of the QOOH· unimolecular dissociation rates at a wide range of energies aligned with theoretical predictions. Unimolecular decay was enhanced by heavy-atom tunneling involving O-O elongation and C-C-O angle contraction.

SCIENCE (2021)

Article Computer Science, Interdisciplinary Applications

KinBot: Automated stationary point search on potential energy surfaces

Ruben Van de Vijver et al.

COMPUTER PHYSICS COMMUNICATIONS (2020)

Article Chemistry, Physical

The Molpro quantum chemistry package

Hans-Joachim Werner et al.

JOURNAL OF CHEMICAL PHYSICS (2020)

Article Thermodynamics

High-pressure pyrolysis and oxidation of DME and DME/CH4

Hamid Hashemi et al.

COMBUSTION AND FLAME (2019)

Review Physics, Condensed Matter

The atomic simulation environment-a Python library for working with atoms

Ask Hjorth Larsen et al.

JOURNAL OF PHYSICS-CONDENSED MATTER (2017)

Article Thermodynamics

A theoretical study of cyclic ether formation reactions

John Bugler et al.

PROCEEDINGS OF THE COMBUSTION INSTITUTE (2017)

Article Thermodynamics

Influence of oxygenation in cyclic hydrocarbons on chain-termination reactions from R + O2: tetrahydropyran and cyclohexane

Brandon Rotavera et al.

PROCEEDINGS OF THE COMBUSTION INSTITUTE (2017)

Article Thermodynamics

An ignition delay time and chemical kinetic modeling study of the pentane isomers

John Bugler et al.

COMBUSTION AND FLAME (2016)

Article Multidisciplinary Sciences

Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)

John D. Savee et al.

SCIENCE (2015)

Article Chemistry, Physical

Progress in Understanding Low-Temperature Organic Compound Oxidation Using a Jet-Stirred Reactor

Olivier Herbinet et al.

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS (2014)

Article Chemistry, Physical

Directly measuring reaction kinetics of •QOOH - a crucial but elusive intermediate in hydrocarbon autoignition

Judit Zador et al.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2013)

Review Thermodynamics

Kinetics of elementary reactions in low-temperature autoignition chemistry

Judit Zador et al.

PROGRESS IN ENERGY AND COMBUSTION SCIENCE (2011)