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Issue 38, 2015
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Even–odd product variation of the Cn+ + D2 (n = 4–9) reaction: complexity of the linear carbon cation electronic states

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Abstract

We have studied reactions between linear Cn+ (n = 4–9) and D2, using ion mobility mass spectrometry techniques and quantum chemical calculations in order to understand the complex reactivity of the linear cluster cations. Only linear CnD+ products were observed for the odd (n = 5, 7, 9) linear clusters, while CnD2+ was the main product for the even clusters. For the reaction rate constants determined for these two channels, we obtained the following two features: (1) the rate constant decreases with the size n, and (2) even-sized clusters have lower rate constants than neighboring odd-sized clusters. In the theoretical calculations using the CCSD(T) and B3LYP methods with the cc-pVTZ basis, we found that a low lying 2Σ state in odd clusters may play an important role in these reactions. This opposes the previous interpretation that the 2Πg/u state is the dominant electronic state for linear Cn+ (n = 4–9) clusters. We showed that a barrierless radical abstraction forming CnD+ occurs through a direct head on approach for the 2Σ state Cn+. In contrast, a carbene-like insertion forming CnD2+ occurs through a sideways approach for the 2Πg/u state Cn+. We have concluded that the higher rate constants for the odd clusters come from the existence of symmetry broken 2Σ states which are absent in even linear clusters.

Graphical abstract: Even–odd product variation of the Cn+ + D2 (n = 4–9) reaction: complexity of the linear carbon cation electronic states

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Publication details

The article was received on 30 Jul 2015, accepted on 18 Aug 2015 and first published on 19 Aug 2015


Article type: Paper
DOI: 10.1039/C5CP04480D
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 24810-24819
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    Even–odd product variation of the Cn+ + D2 (n = 4–9) reaction: complexity of the linear carbon cation electronic states

    K. Koyasu, T. Ohtaki, J. Bing, K. Takahashi and F. Misaizu, Phys. Chem. Chem. Phys., 2015, 17, 24810
    DOI: 10.1039/C5CP04480D

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