Effects of collision energy and vibrational excitation of CH3+ cations on its reactivity with hydrocarbons: But-2-yne CH3CCCH3 as reagent partner

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00482743" target="_blank" >RIV/61388955:_____/17:00482743 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1063/1.4990514" target="_blank" >http://dx.doi.org/10.1063/1.4990514</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/1.4990514" target="_blank" >10.1063/1.4990514</a>

Result language

angličtina

Original language name

Effects of collision energy and vibrational excitation of CH3+ cations on its reactivity with hydrocarbons: But-2-yne CH3CCCH3 as reagent partner

Original language description

The methyl carbocation is ubiquitous in gaseous environments, such as planetary ionospheres, cometary comae, and the interstellar medium, as well as combustion systems and plasma setups for technological applications. Here we report on a joint experimental and theoretical study on the mechanism of the reaction CH3+ + CH3CCCH3 (but-2-yne, also known as dimethylacetylene), by combining guided ion beam mass spectrometry experiments with ab initio calculations of the potential energy hypersurface. Such a reaction is relevant in understanding the chemical evolution of Saturn's largest satellite, Titan. Two complementary setups have been used: in one case, methyl cations are generated via electron ionization, while in the other case, direct vacuum ultraviolet photoionization with synchrotron radiation of methyl radicals is used to study internal energy effects on the reactivity. Absolute reactive cross sections have been measured as a function of collision energy, and product branching ratios have been derived. The two most abundant products result from electron and hydride transfer, occurring via direct and barrierless mechanisms, while other channels are initiated by the electrophilic addition of the methyl cation to the triple bond of but-2-yne. Among the minor channels, special relevance is placed on the formation of C5H7+, stemming from H-2 loss from the addition complex. This is the only observed condensation product with the formation of new C-C bonds, and it might represent a viable pathway for the synthesis of complex organic species in astronomical environments and laboratory plasmas. Published by AIP Publishing.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

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Volume of the periodical

147

Issue of the periodical within the volume

15

Country of publishing house

US - UNITED STATES

Number of pages

14

Pages from-to

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UT code for WoS article

000413398700039

EID of the result in the Scopus database

2-s2.0-85031736473