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A Direct Link from the Gas to the Condensed Phase: A Rotational Spectroscopic Study of 2,2,2‐Trifluoroethanol Trimers
Author(s) -
Thomas Javix,
Seifert Nathan A.,
Jäger Wolfgang,
Xu Yunjie
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201612161
Subject(s) - conformational isomerism , chemistry , crystallography , ab initio , rotational spectroscopy , hydrogen bond , ab initio quantum chemistry methods , ternary operation , cluster (spacecraft) , gas phase , phase (matter) , molecule , organic chemistry , computer science , programming language
Rotational spectra of the three most stable conformers ( I , II , III ) of the ternary 2,2,2‐trifluoroethanol (TFE) cluster were measured using Fourier transform microwave spectrometers, and unambiguously assigned with the aid of ab initio calculations. The most stable conformer, I , contains one trans‐TFE subunit which is unstable in its isolated gas phase form. The study offers new insights into how the trans conformation is stabilized in TFE clusters of increasing size, and eventually becomes a dominant conformation in the liquid phase. A detailed analysis shows that while O−H⋅⋅⋅O−H and O−H⋅⋅⋅F−C hydrogen bonds are the most significant attractive interactions which stabilize all three conformers, the main driving force for the stability of I over III , which has all gauche‐TFE subunits, is the attractive interaction of C−F⋅⋅⋅F−C contact pairs. A new type of three‐point F⋅⋅⋅F⋅⋅⋅F attractive contact interaction is also identified.