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Effects of Mixing between Short-chain and Branched-chain Alcohols in Protonated Clusters

Abstract

The previous analysis on the neat protonated branched-chain alcohol clusters has revealed the impact of steric repulsion and dispersion of the bulky alkyl group to the hydrogen-bonded (H-bonded) structures and their temperature-dependence. To further understand the influence of the alkyl groups in H-bonded clusters, we studied the mixing of the two extremes of alcohols, methanol (MeOH) and tert-butyl alcohol (t-BuOH), with an excess proton. Infrared spectroscopy and structural search of first principle calculations on the size-selected clusters, H+(MeOH)m(t-BuOH)t (m + t = 4 and 5), were conducted. Temperature-dependence of the dominant H-bonded structures was explored by the Ar-tagging technique and quantum harmonic superposition approach. By introducing the dispersion-corrected density functional theory methods, it was shown that effects of dispersion due to the bulky alkyl groups in the mixed clusters cannot be ignored for t ≥ 2 . The computational results qualitatively depicted the characteristics of the observed IR spectra, but overestimation of temperature-dependence with dispersion correction was clearly seen due to the unbalanced correction between linear H-bonded structures and compact cyclic ones. These results demonstrate the importance of extensive investigation and benchmarks on different levels of theory, and a properly sampled structure database is crucial to evaluate theoretical models.

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Supplementary files

Article information


Submitted
27 Feb 2020
Accepted
07 May 2020
First published
08 May 2020

Phys. Chem. Chem. Phys., 2020, Accepted Manuscript
Article type
Paper

Effects of Mixing between Short-chain and Branched-chain Alcohols in Protonated Clusters

P. Hsu, T. Shinkai, P. Tai, A. Fujii and J. Kuo, Phys. Chem. Chem. Phys., 2020, Accepted Manuscript , DOI: 10.1039/D0CP01116A

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