Cooperative and anticooperative mixed trimers of HCl and methanol

Abstract

In the hydrogen-bonded complex between two HCl molecules and one methanol unit, there are two isomers with similar energies. A cyclic isomer profits from hydrogen bond cooperativity, whereas a converging structure, in which both HCl molecules bind to the lone pairs of methanol, profits from the good acceptor quality of methanol. The latter compensates for anticooperative three-body forces, which arise from the competition of the HCl units for acceptor electron density. This theoretical prediction is supported by FT-IR spectra of supersonic jet expansions, in which both mixed trimers are tentatively assigned along with the mixed dimer of HCl and methanol based on their O–H and Cl–H stretching bands.