English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/110207
Compartir / Impacto:
Estadísticas
Add this article to your Mendeley library MendeleyBASE
Citado 2 veces en Web of Knowledge®  |  Ver citas en Google académico
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar otros formatos: Exportar EndNote (RIS)Exportar EndNote (RIS)Exportar EndNote (RIS)
Título

Comparative dynamics of the two channels of the reaction of D + MuH

Autor Aoiz, F. Javier ; Aldegunde, J.; Herrero, Víctor J. ; Sáez Rábanos, Vicente
Fecha de publicación 2014
EditorRoyal Society of Chemistry (Great Britain)
Citación Physical Chemistry Chemical Physics 16: 9808- 9818 (2014)
ResumenThe dynamics of the asymmetric D + MuH (Mu = Muonium) reaction leading to Mu exchange, DMu + H, and H abstraction, DH + Mu, channels has been investigated using time-independent quantum mechanical (QM) calculations. Reaction probabilities, cross sections, cumulative reaction probabilities, and rate coefficients were determined for the two exit channels of the reaction. Quasiclassical trajectory (QCT) calculations were also performed in order to check the reliability of the method for this reaction and to discern the genuine quantum effects. Overall, the Mu exchange channel exhibits more structured reaction probabilities and cross sections with much larger rate coefficients than the H abstraction counterpart. Over the 100-1000 K temperature interval considered in this study, the QM rate coefficients for the Mu exchange vary between ≈5 × 10-15 and 2 × 10-11 cm 3 s-1 and those for the generation of DH + Mu between 2 × 10-18 and 3.5 × 10-12 cm3 s -1. In common with the rest of the isotopologues of the H + H 2 system, the height of the respective barriers in the collinear (symmetric stretch) vibrationally adiabatic potential energy curves matches the classical total energy threshold very accurately. Indeed, the lower and narrower vibrationally adiabatic collinear barrier as compared with that for the DH + Mu formation determines the preponderance of the DMu + H channel. Comparison of QM and QCT results and their analysis show that tunneling accounts for the reactivity at energies below the height of these barriers and that its effect on the rate coefficients becomes appreciable below 300 K. As expected, with growing temperature the contribution of tunneling to the global reactivity decreases markedly, but the rate coefficients are still much higher for the Mu exchange channel due to the effect of MuH rotational excitation that boosts the formation of DMu while diminishing the H abstraction channel that leads to DH formation. The analysis of the thermal cumulative reaction probabilities of the two channels indicates that at the lowest energies/temperatures the reaction into the DH + Mu channel takes place via 'leakage' from collisions proceeding along the DMu + H reaction path. © the Partner Organisations 2014.
URI http://hdl.handle.net/10261/110207
DOI10.1039/c3cp53908c
Identificadoresdoi: 10.1039/c3cp53908c
issn: 1463-9076
Aparece en las colecciones: (CFMAC-IEM) Artículos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
accesoRestringido.pdf15,38 kBAdobe PDFVista previa
Visualizar/Abrir
Mostrar el registro completo
 



NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.