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dc.contributor.authorFerro Costas, David
dc.contributor.authorMartínez Núñez, Emilio
dc.contributor.authorRodríguez Otero, Jesús
dc.contributor.authorCabaleiro Lago, Enrique Manuel
dc.contributor.authorEstévez, Carlos M.
dc.contributor.authorFernández Rodríguez, Berta
dc.contributor.authorFernández Ramos, Antonio
dc.contributor.authorVázquez Rodríguez, Saulo Angel
dc.identifier.citationFerro-Costas, D., Martínez-Núñez, E., Rodríguez-Otero, J., Cabaleiro-Lago, E., Estévez, C., & Fernández, B. et al. (2018). Influence of Multiple Conformations and Paths on Rate Constants and Product Branching Ratios. Thermal Decomposition of 1-Propanol Radicals. The Journal Of Physical Chemistry A, 122(21), 4790-4800. doi: 10.1021/acs.jpca.8b02949
dc.description.abstractThe potential energy surface involved in the thermal decomposition of 1-propanol radicals was investigated in detail using automated codes (tsscds2018 and Q2DTor). From the predicted elementary reactions, a relevant reaction network was constructed to study the decomposition at temperatures in the range 1000–2000 K. Specifically, this relevant network comprises 18 conformational reaction channels (CRCs), which in general exhibit a large wealth of conformers of reactants and transition states. Rate constants for all the CRCs were calculated using two approaches within the formulation of variational transition-state theory (VTST), as incorporated in the TheRa program. The simplest, one-well (1W) approach considers only the most stable conformer of the reactant and that of the transition state. In the second, more accurate approach, contributions from all the reactant and transition-state conformers are taken into account using the multipath (MP) formulation of VTST. In addition, kinetic Monte Carlo (KMC) simulations were performed to compute product branching ratios. The results show significant differences between the values of the rate constants calculated with the two VTST approaches. In addition, the KMC simulations carried out with the two sets of rate constants indicate that, depending on the radical considered as reactant, the 1W and the MP approaches may display different qualitative pictures of the whole decomposition process
dc.description.sponsorshipThis work was partially supported by the Consellería de Cultura, Educación e Ordenación Universitaria e da Consellería de Economía, Emprego e Industria (Axuda para Consolidación e Estructuración de unidades de investigación competitivas do Sistema Universitario de Galicia, Xunta de Galicia ED431C 2017/17 & Centro singular de investigación de Galicia acreditación 2016-2019, ED431G/09), the Ministerio de Economía y Competitividad of Spain (Research Grant No CTQ2014-58617-R), and the European Regional Development Fund (ERDF). D.F.-C. also thanks Xunta de Galicia for financial support through a postdoctoral grant. The authors thank “Centro de Supercomputación de Galicia (CESGA)” for the use of their computational facilities
dc.publisherAmerican Chemical Society
dc.relationinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-58617-R/ES/IMULACION DEL PROCESO DE COMBUSTION DE BIOALCOHOLES
dc.rights© 2018 American Chemical Society
dc.titleInfluence of Multiple Conformations and Paths on Rate Constants and Product Branching Ratios. Thermal Decomposition of 1-Propanol Radicals
dc.contributor.affiliationUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
dc.contributor.affiliationUniversidade de Santiago de Compostela. Departamento de Química Física

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