Selective Generation of the Radical Cation Isomers [CH3CN](center dot+) and [CH2CNH](center dot+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F16%3A00467081" target="_blank" >RIV/61388955:_____/16:00467081 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1021/acs.jpca.5b12757" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.5b12757</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.5b12757" target="_blank" >10.1021/acs.jpca.5b12757</a>

Result language

angličtina

Original language name

Selective Generation of the Radical Cation Isomers [CH3CN](center dot+) and [CH2CNH](center dot+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4

Original language description

Experimental and theoretical studies have been carried out to demonstrate the selective generation of two different C2H3N center dot+ isomers, namely, the acetonitrile [CH3CN](center dot+) and the ketenimine [CH2CNH](center dot+) radical cations. Photoionization and dissociative photoionization experiments from different neutral precursors (acetonitrile and butanenitrile) have been performed using vacuum ultraviolet (VUV) synchrotron radiation in the 10-15 eV energy range, delivered by the DESIRS beamline at the SOLEIL storage ring. For butanenitrile (CH3CH2CH2CN) an experimental ionization threshold of 11.29 +/- 0.05 eV is obtained, whereas the appearance energy for the formation of [CH2CNH](center dot+) fragments is 11.52 +/- 0.05 eV. Experimental findings are fully supported by theoretical calculations at the G4 level of theory (ZPVE corrected energies at 0 K), giving a value of 11.33 eV for the adiabatic ionization energy of butanenitrile and an exothermicity of 0.49 for fragmentation into [CH2CNH](center dot+) plus C2H4, hampered by an energy barrier of 0.29 eV. The energy difference between [CH3CN](center dot+) and [CH2CNH](center dot+) is 2.28 eV (with the latter being the lowest energy isomer), and the isomerization barrier is 0.84 eV. Reactive monitoring experiments of the [CH3CN](center dot+) and [CH2CNH](center dot+) isomers with C2H4 have been performed using the CERISES guided ion beam tandem mass spectrometer and exploiting the selectivity of ethylene that gives exothermic charge exchange and proton transfer reactions with [CH3CN](center dot+) but not with [CH2CNH](center dot+) isomers. In addition, minor reactive channels are observed leading to the formation of new C-C bonds upon reaction of [CH3CN](center dot+) with C2H4, and their astrochemical implications are briefly discussed.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

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

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2016

Confidentiality

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

Name of the periodical

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

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Volume of the periodical

120

Issue of the periodical within the volume

27

Country of publishing house

US - UNITED STATES

Number of pages

12

Pages from-to

5041-5052

UT code for WoS article

000379988900051

EID of the result in the Scopus database

2-s2.0-84978630833