Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical

Abstract The reaction mechanisms and kinetics of thiophene oxidation reactions initiated by hydroperoxyl radical, and decomposition of the related intermediates and complexes, have been considered herein by using high-level DFT and ab initio calculations. The main energetic parameters of all station...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Maryam Seyed Sharifi, Hamed Douroudgari, Morteza Vahedpour
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/d0c7c85d56554b859a9ef59c8224c132
Etiquetas:	Agregar Etiqueta Sin Etiquetas, Sea el primero en etiquetar este registro!

id	oai:doaj.org-article:d0c7c85d56554b859a9ef59c8224c132
record_format	dspace
spelling	oai:doaj.org-article:d0c7c85d56554b859a9ef59c8224c1322021-12-02T16:07:04ZChemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical10.1038/s41598-021-92221-z2045-2322https://doaj.org/article/d0c7c85d56554b859a9ef59c8224c1322021-06-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-92221-zhttps://doaj.org/toc/2045-2322Abstract The reaction mechanisms and kinetics of thiophene oxidation reactions initiated by hydroperoxyl radical, and decomposition of the related intermediates and complexes, have been considered herein by using high-level DFT and ab initio calculations. The main energetic parameters of all stationary points of the suggested potential energy surfaces have been computed at the BD(T) and CCSD(T) methods, based on the geometries optimized at the B3LYP/6-311 + g(d,p) level of theory. Rate constants of bimolecular reactions (high-pressure limit rate constants) at temperatures from 300 to 3000 K for the first steps of the title reaction have been obtained through the conventional transition state theory (TST), while the pressure dependent rate constants and the rate constants of the second and other steps have been calculated employing the Rice–Ramsperger–Kassel–Marcus/Master equation (RRKM/ME). The results show that the rate constants of addition to α and β carbons have positive temperature dependence and negative pressure dependence. It is found that the additions of HO2 to the α and β carbons of thiophene in the initial steps of the title reaction are the most favored pathways. Also, the addition to the sulfur atom has a minor contribution. But, all efforts for simulating hydrogen abstraction reactions have been unsuccessful. In this complex oxidation reaction, about 12 different products are obtained, including important isomers such as thiophene-epoxide, thiophene-ol, thiophene-oxide, oxathiane, and thiophenone. The calculated total rate constants for generation of all minimum stationary points show that the addition reactions to the α and β carbons are the fastest among all at temperatures below 1000 K, while the proposed multi-step parallel reactions are more competitive at temperatures above 1200 K. Furthermore, important inter-and intra-molecular interactions for some species have been investigated by two well-known quantum chemistry method, the NBO and AIM analyses. Thermochemical properties such as free energy, enthalpy, internal energy, and entropy for thiophene and hydroperoxyl radical and related species in the simulated reactions have been predicted using a combination of the B3LYP and BD(T) methods.Maryam Seyed SharifiHamed DouroudgariMorteza VahedpourNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-20 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Maryam Seyed Sharifi Hamed Douroudgari Morteza Vahedpour Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
description	Abstract The reaction mechanisms and kinetics of thiophene oxidation reactions initiated by hydroperoxyl radical, and decomposition of the related intermediates and complexes, have been considered herein by using high-level DFT and ab initio calculations. The main energetic parameters of all stationary points of the suggested potential energy surfaces have been computed at the BD(T) and CCSD(T) methods, based on the geometries optimized at the B3LYP/6-311 + g(d,p) level of theory. Rate constants of bimolecular reactions (high-pressure limit rate constants) at temperatures from 300 to 3000 K for the first steps of the title reaction have been obtained through the conventional transition state theory (TST), while the pressure dependent rate constants and the rate constants of the second and other steps have been calculated employing the Rice–Ramsperger–Kassel–Marcus/Master equation (RRKM/ME). The results show that the rate constants of addition to α and β carbons have positive temperature dependence and negative pressure dependence. It is found that the additions of HO2 to the α and β carbons of thiophene in the initial steps of the title reaction are the most favored pathways. Also, the addition to the sulfur atom has a minor contribution. But, all efforts for simulating hydrogen abstraction reactions have been unsuccessful. In this complex oxidation reaction, about 12 different products are obtained, including important isomers such as thiophene-epoxide, thiophene-ol, thiophene-oxide, oxathiane, and thiophenone. The calculated total rate constants for generation of all minimum stationary points show that the addition reactions to the α and β carbons are the fastest among all at temperatures below 1000 K, while the proposed multi-step parallel reactions are more competitive at temperatures above 1200 K. Furthermore, important inter-and intra-molecular interactions for some species have been investigated by two well-known quantum chemistry method, the NBO and AIM analyses. Thermochemical properties such as free energy, enthalpy, internal energy, and entropy for thiophene and hydroperoxyl radical and related species in the simulated reactions have been predicted using a combination of the B3LYP and BD(T) methods.
format	article
author	Maryam Seyed Sharifi Hamed Douroudgari Morteza Vahedpour
author_facet	Maryam Seyed Sharifi Hamed Douroudgari Morteza Vahedpour
author_sort	Maryam Seyed Sharifi
title	Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
title_short	Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
title_full	Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
title_fullStr	Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
title_full_unstemmed	Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
title_sort	chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/d0c7c85d56554b859a9ef59c8224c132
work_keys_str_mv	AT maryamseyedsharifi chemicalinsightsintotheatmosphericoxidationofthiophenebyhydroperoxylradical AT hameddouroudgari chemicalinsightsintotheatmosphericoxidationofthiophenebyhydroperoxylradical AT mortezavahedpour chemicalinsightsintotheatmosphericoxidationofthiophenebyhydroperoxylradical
_version_	1718384806965805056

Chemical insights into the atmospheric oxidation of thiophene by hydroperoxyl radical

Ejemplares similares