Chirality Synchronization in Trifluoroethanol Dimer Revisited: The Missing Heterochiral Dimer

Chirality self-recognition in the dimer of transient chiral 2,2,2-trifluoroethanol (TFE) is studied using chirped pulse and cavity-based Fourier transform microwave spectroscopy with the aid of ab initio calculations. The broad-band and extreme high-resolution capabilities enable us to assign rotational spectra of the most stable homo- and heterochiral dimers and analyze their structural and dynamical properties in detail. A strong preference for the homochiral over the heterochiral diastereomers is observed. The current study unambiguously identifies the structure of the most stable homochiral dimer and supports the identification by the previous low-resolution infrared study. More importantly, it also indisputably detects the so far elusive, most stable heterochiral dimer.