Chirality recognition between largely rigid molecules can be applied as ab enchmark for the description of intermolecular forces by theoretical methods,b ecause one constituent is merely mirrored, so other deficits of the methods such as neglect of anharmonicity should mostly cancel. To test this approach, mixed OH···p-bridged dimers between the enantiomers of the bicyclic monoterpene a-pinene and the chiral secondary alcohols borneol, a-fenchol, isopinocampheol, and 1-phenylethanol were formed in as upersonic jet and probed by linear FTIR spectroscopy. With borneol and afenchol, pronounced shifts in the hydroxyl stretching frequencies upon exchange of the handedness are observed. From three tested density functionals,only B3LYP-D3(BJ) is able to predict these diastereomeric shifts in as atisfactory manner, while M06-2X and wB97X-D fall short.Chirality recognition, the ability of chiral objects to distin-Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
Chirality recognition between largely rigid molecules can be applied as ab enchmark for the description of intermolecular forces by theoretical methods,b ecause one constituent is merely mirrored, so other deficits of the methods such as neglect of anharmonicity should mostly cancel. To test this approach, mixed OH···p-bridged dimers between the enantiomers of the bicyclic monoterpene a-pinene and the chiral secondary alcohols borneol, a-fenchol, isopinocampheol, and 1-phenylethanol were formed in as upersonic jet and probed by linear FTIR spectroscopy. With borneol and afenchol, pronounced shifts in the hydroxyl stretching frequencies upon exchange of the handedness are observed. From three tested density functionals,only B3LYP-D3(BJ) is able to predict these diastereomeric shifts in as atisfactory manner, while M06-2X and wB97X-D fall short.Chirality recognition, the ability of chiral objects to distin-Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.