Revisiting conformations of methyl lactate in water and methanol

The recently developed efficient protocols to implicit [Grimme et al., J. Phys. Chem. A 125, 4039-4054 (2021)] and explicit quantum mechanical modeling of non-rigid molecules in solution [Katsyuba et al., J. Phys. Chem. B 124, 6664-6670 (2020)] are applied to methyl lactate (ML). Building upon this work, a new combination scheme is proposed to incorporate solvation effects for the computation of infrared (IR) absorption spectra. Herein, Boltzmann populations calculated for implicitly solvated single conformers are used to weight the IR spectra of explicitly solvated clusters with a size of typically ten solvent molecules, i.e., accounting for the first solvation shell. It is found that in water and methanol, the most abundant conformers of ML are structurally modified relative to the gas phase, where the major form is ML1, in which the syn conformation of the -OH moiety is stabilized by a OHO=C intramolecular hydrogen bond (HB). In solution, this syn conformation transforms to the gauche form because the intramolecular HB is disrupted by explicit water molecules that form intermolecular HBs with the hydroxyl and carbonyl groups. Similar changes induced by the gas-solution transition are observed for the minor conformers, ML2 and/or ML3, characterized by OHOCH3 intramolecular HB in the gas phase. The relative abundance of ML1 is shown to decrease from similar to 96% in gas to similar to 51% in water and similar to 92% in methanol. The solvent strongly influences frequencies, IR intensities, and normal modes, resulting in qualitatively different spectra compared to the gas phase. Some liquid-state conformational markers in the fingerprint region of IR spectra are revealed.

Automated summary

Efficient protocols for implicit and explicit quantum mechanical modeling were applied to methyl lactate, proposing a new combination scheme for calculating IR absorption spectra. The solvent significantly influenced the structural changes in different conformers of ML in water and methanol, leading to qualitatively different spectra compared to the gas phase. Liquid-state conformational markers were revealed in the fingerprint region of IR spectra.