The kinetics of the HCCO + NO2 reaction were investigated using a laser photolysis/infrared diode laser absorption technique. Ethyl ethynyl ether (C2H5OCCH) was used as the HCCO radical precursor. Transient infrared detection of the HCCO radical was used to determine a total rate constant fit to the following expression: k1= (2.43 +/- 0.26) x 10(-11) exp[(171.1 +/- 36.9)/T] cm3 molecule(-1) s(-1) over the temperature range of 298-423 K. Transient infrared detection of CO, CO2, and HCNO products was used to determine the following branching ratios at 298 K: phi(HCO + NO + CO) = 0.60 +/- 0.05 and phi(HCNO + CO2) = 0.40 +/- 0.05.
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http://dx.doi.org/10.1021/jp0580423 | DOI Listing |
Chemphyschem
February 2024
School of Chemical Engineering, Guizhou Institute of Technology, Guiyang, Guizhou, 550003, P. R. China.
A detailed and accurate combustion reaction mechanism is crucial for understanding the nature of fuel combustion. In this work, a theoretical study of reaction HCCO+HO using M06-2X/6-311++G(d,p) for geometry optimization and combined methods based on spin-unrestricted CCSD(T)/CBS level of theory with basis set extrapolation from MP2/aug-cc-pVnZ (n=T and Q) for energy calculations were performed. The temperature- and pressure-dependent rate coefficients at 300-2000 K and 0.
View Article and Find Full Text PDFJ Phys Chem A
August 2023
School of Chemistry, University of Birmingham, Edgbaston B15 2TT, United Kingdom.
The first theoretical results regarding the gas-phase reaction mechanism and kinetics of the CH (XΠ) + OCS reaction are presented here. This reaction has a proposed importance in the removal of OCS in regions of the interstellar medium (ISM) and has the potential to form the recently observed HCS/HSC isomers, with both constitutional isomers having recently been observed in the L483 molecular cloud in a 40:1 ratio. Statistical rate theory simulations were performed on stationary points along the reaction potential energy surface (PES) obtained from calculations at the RO-CCSD(T)/aug-cc-pV(Q+d)Z//M06-2X-D3/aug-cc-pV(Q+d)Z level of theory over the temperature and total density range of 150-3000 K and 10-10 cm, respectively, using a Master Equation analysis.
View Article and Find Full Text PDFJ Phys Chem A
June 2023
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
The reaction of atomic carbon, C(P), with HCO has been investigated using the direct dynamics trajectory surface hopping (DDTSH) method with Tully's fewest switches algorithm. The lowest lying ground triplet and single states are considered for the dynamics study at a reagent collision energy of 8.0 kcal/mol.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2022
Centre for Theoretical Chemistry and Physics (CTCP), The New Zealand Institute for Advanced Study (NZIAS), Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New Zealand.
CO capture, conversion and storage belong to the holy grail of environmental science. We therefore explore an important photochemical hydride transfer reaction of benzimidazoline derivatives with CO in a polar solvent (dimethylsulfoxide) by quantum-chemical methods. While the excited electronic state undergoing hydride transfer to formate (HCOO) shows a higher reaction path barrier compared to the ground state, a charge-transfer can occur in the near-UV region with nearly barrierless access to the products involving a conical intersection between both electronic states.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2019
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
The O(P) + CH reaction is the first step in acetylene oxidation. The accurate kinetic data and the understanding of the reaction dynamics is of great importance. To this end, a full-dimensional global potential energy surface (PES) for the ground triplet state of the O(P) + CH reaction is constructed based on approximately 85 000 ab initio points calculated at the level of explicitly correlated unrestricted coupled cluster single, double, and perturbative triple excitations with the explicitly correlated polarized valence triple zeta basis set (UCCSD(T)-F12b/VTZ-F12).
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