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Hydrogen bond network structures of protonated short-chain alcohol clusters


Because of the hydrogen bond coordination property of alcohols, their possible hydrogen bond network structures are categorized into only several types. Therefore, gas phase clusters of alcohols can be a very simple model system to examine the property of hydrogen bond networks, such as structural development with cluster size and its temperature dependence. In this perspective, we focus on the structure study on protonated short-chain alcohol clusters, of which excess proton (charge) enables us size-selective spectroscopy in combination with mass spectrometric techniques. Size-selective infrared spectroscopy and theoretical multi-scale isomer search are applied to protonated clusters of methanol, which is a prototype of short-chain alcohols, and their hydrogen bond network development is elucidated in detail. Complete isomer population switching with elevation of temperature is predicted by the quantum harmonic superposition approximation, and this isomer switching is evidenced by the remarkable temperature (internal vibrational energy) dependence of the observed infrared spectra. The characteristics of the temperature dependence of protonated methanol are compared with water and neutral methanol. In addition, possible hydrogen bond networks of methanolated ions are discussed on the basis of the results of protonated methanol. Stepwise change of internal energy of the clusters with the inert gas tagging is demonstrated. Convergence of the hydrogen bond network to the bulk-like one at the large size clusters is also discussed. Hydrogen bond structures of the protonated clusters of longer normal alkyl chain alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) are determined by the comparison of their infrared spectra with those of the protonated methanol clusters. It is demonstrated that the normal alkyl chain hardly interferes with the most stable hydrogen bond structure though a few exceptional cases are also found. These exceptions cases serve as good model systems for further theoretical and computational studies.

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Publication details

The article was received on 01 Dec 2017, accepted on 05 Mar 2018 and first published on 05 Mar 2018

Article type: Perspective
DOI: 10.1039/C7CP08072G
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Hydrogen bond network structures of protonated short-chain alcohol clusters

    A. Fujii, N. Sugawara, P. Hsu, T. Shimamori, Y. C. Li, T. Hamashima and J. Kuo, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C7CP08072G

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