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Competition between hydrogen bonds and van der Waals force in intermolecular structure formation of protonated branched-chain alcohol clusters

Abstract

To investigate influence of bulky alkyl groups on hydrogen-bonded (H-bonded) network structures of alcohols, infrared (IR) spectra of protonated clusters of 2-propanol (2-PrOH) and tert-butyl alcohol (t-BuOH) were observed in the OH and CH stretch region. In addition, by using the variation of the tag species, the temperature dependence profile of the isomer population of H+(t-BuOH)n was revealed. Extensive search for stable isomers was performed by the dispersion-corrected density functional theories and temperature-dependent IR spectral simulations were done based on harmonic superposition approximation. The computational results qualitatively agree with the observed size and temperature dependence of the H-bonded network structures of these protonated bulky alcohol clusters. However, the difficulty of the quantitative evaluation of dispersion was also demonstrated. It was shown that H+(2-PrOH)n (n = 4 - 7) have essentially the same network structures as those of the protonated normal alcohol clusters studied so far. On the other hands, H+(t-BuOH)n (n = 4 - 8) showed a clear preference of the smaller-membered ring structures, that is very different from the preference of the protonated normal alcohol clusters. The origin of the different structure preference was discussed in terms of the steric effect and dispersion.

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Publication details

The article was received on 16 Aug 2018, accepted on 12 Sep 2018 and first published on 12 Sep 2018


Article type: Paper
DOI: 10.1039/C8CP05222K
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Competition between hydrogen bonds and van der Waals force in intermolecular structure formation of protonated branched-chain alcohol clusters

    N. Sugawara, P. Hsu, A. Fujii and J. Kuo, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP05222K

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