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CHF3…H2O complex revisited: a matrix isolation and ab initio study

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Abstract

The structural and spectroscopic features of the CHF3…H2O complex have been investigated using high-level ab initio calculations and IR matrix isolation spectroscopy. In contrast to previous findings, the computations at the CCSD(T)/L3a_3 and MP2/L3a_3 levels of theory revealed only one structure of the complex stabilized by two C-H…O and O-H…F hydrogen bonds. The interaction energy extrapolated to a complete basis set with ZPVE and BSSE corrections is 2.73 kcal/mol at the CCSD(T) level, taking into account the zero-point vibrational energy (ZPVE) and basis set superposition error (BSSE) corrections. According to Bader’s analysis, complex exhibits a cyclic structure, which confirms the existence of ring critical point as well as bond critical points in the system. The calculated complexation-induced shifts of the fluoroform fundamentals are in good agreement with the matrix isolation results. In addition to previously reported IR absorptions of the complex, the feature corresponding to the C-F bending mode of CHF3…H2O was first observed, in good correlation with the computational predictions.

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Acknowledgments

The Joint Supercomputer Center of the Russian Academy of Sciences (JSCC RAS) is acknowledged for granting computation resources. The authors are indebted to I.V. Tyulpina and E. S. Shiryaeva for experimental assistance.

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  1. Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia, 119991

    Ilya S. Sosulin, Daniil A. Tyurin & Vladimir I. Feldman

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  1. Ilya S. Sosulin
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Correspondence to Vladimir I. Feldman.

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Sosulin, I.S., Tyurin, D.A. & Feldman, V.I. CHF3…H2O complex revisited: a matrix isolation and ab initio study. Struct Chem 30, 559–566 (2019). https://doi.org/10.1007/s11224-018-1232-z

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