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dc.contributor.authorMendes, Jorge
dc.contributor.authorZhou, Chong-Wen
dc.contributor.authorCurran, Henry J.
dc.date.accessioned2016-11-09T11:44:39Z
dc.date.available2016-11-09T11:44:39Z
dc.date.issued2014-05-30
dc.identifier.citationMendes, J,Zhou, CW,Curran, HJ (2014) 'Theoretical study of the rate constants for the hydrogen atom abstraction reactions of esters with •OH radicals'. Journal Of Physical Chemistry A, 118 :4889-4899.en_IE
dc.identifier.issn1520-5215
dc.identifier.urihttp://hdl.handle.net/10379/6148
dc.descriptionJournal articleen_IE
dc.description.abstractA systematic investigation of the rate constants for hydrogen atom abstraction reactions by hydroxyl radicals on esters has been performed. The geometry optimizations and frequency calculations were obtained using the second-order Moller-Plesset method with the 6-311G(d,p) basis set. The same method was also used in order to determine the dihedral angle potential for each individual hindered rotor in each reactant and transition state. Intrinsic reaction coordinate calculations were used in order to connect each transition state to the corresponding local minimum. For the reactions of methyl ethanoate with an (OH)-O-center dot radical, the relative electronic energies were calculated using the G3 and the CCSD(T)/cc-pVXZ (where X = D, T, and Q) methods, which were extrapolated to the complete basis set (CBS) limit. The electronic energies obtained using the G3 method were then benchmarked against the CBS results and were found to be within 1 kcal mol(-1) of one another. The high-pressure limit rate constants for every reaction channel were calculated by conventional transition-state theory, with an asymmetric Eckart tunneling correction, using the energies obtained with the G3 method. We report the individual, average, and total rate constants in the temperature range from 500 to 2200 K. Our calculated results are within a factor of 2 for methyl ethanoate and between 40% to 50% for methyl propanoate and methyl butanoate when compared to previously reported experimental data.en_IE
dc.description.sponsorshipScience Foundation Ireland (Grant no. 08/IN1./I2055)en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherAmerican Chemical Societyen_IE
dc.relation.ispartofJournal Of Physical Chemistry Aen
dc.subjectVariational transition stateen_IE
dc.subjectn-Butanolen_IE
dc.subjectMethyl butanoateen_IE
dc.subjectOxidationen_IE
dc.subjectKineticsen_IE
dc.subjectPropanoateen_IE
dc.subjectBarrieren_IE
dc.subjectModelen_IE
dc.titleTheoretical study of the rate constants for the hydrogen atom abstraction reactions of esters with •OH radicalsen_IE
dc.typeArticleen_IE
dc.date.updated2016-10-20T09:26:55Z
dc.identifier.doi10.1021/jp5029596
dc.local.publishedsourcehttp://dx.doi.org/10.1021/jp5029596en_IE
dc.description.peer-reviewedpeer-reviewed
dc.contributor.funder|~|
dc.internal.rssid6971437
dc.local.contactHenry Curran, Dept Of Chemistry, Room 215, Arts/Science Building, Nui Galway. 3856 Email: henry.curran@nuigalway.ie
dc.local.copyrightcheckedNo
dc.local.versionACCEPTED
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