Rovibronic signatures of molecular aggregation in the gas phase: subtle homochirality trends in the dimer, trimer and tetramer of benzyl alcohol.
View/ Open
Date
2021-10-27Author
Medel, Robert
Camiruaga Leza, Ander
Saragi, Rizalina Tama
Pinacho Davidson, Pedro Pablo
Pérez, Cristóbal
Schnell, Melanie
Lesarri, Alberto
Suhm, Martin A.
Fernández, José
Metadata
Show full item record
Physical chemistry chemical physics 23(41) : 23610-23624 (2021)
Abstract
[EN]Molecular aggregation is of paramount importance in many chemical processes, including those in living beings. Thus, characterization of the intermolecular interactions is an important step in its understanding. We describe here the aggregation of benzyl alcohol at the molecular level, a process governed by a delicate equilibrium between OHMIDLINE HORIZONTAL ELLIPSISO and OHMIDLINE HORIZONTAL ELLIPSIS pi hydrogen bonds and dispersive interactions. Using microwave, FTIR, Raman and mass-resolved double-resonance IR/UV spectroscopic techniques, we explored the cluster growth up to the tetramer and found a complex landscape, partly due to the appearance of multiple stereoisomers of very similar stability. Interestingly, a consistently homochiral synchronization of transiently chiral monomer conformers was observed during cluster growth to converge in the tetramer, where the fully homochiral species dominates the potential energy surface. The data on the aggregation of benzyl alcohol also constitute an excellent playground to fine-tune the parameters of the most advanced functionals.