Solvent effects on acid-base complexes. What is more important: A macroscopic reaction field or solute-solvent interactions?

Abstract

Can the geometry of an acid-base complex in solution be reproduced in calculations using an implicit accounting for the solvent effect in the form of a macroscopic reaction field? The answer is, "Yes, it can." Is this field equal to the real electric field experienced by the complex in solution? The answer is, "No, it is not." How can the geometry be correct under wrong conditions? This question is answered using density functional theory modeling of geometric and NMR parameters of pyridine⋯HF⋯(HCF3)n adducts in the absence and presence of an external electric field. This adduct under field approach shows that the N⋯H distance is a function of the H-F distance whatever method is used to change the geometry of the latter. An explicit account for solute-solvent interactions is required to get a realistic value of the solvent reaction field. Besides that, this approach reveals how certain NMR parameters depend on the solvent reaction field, the solute-solvent interactions, and the geometry of the N⋯H-F hydrogen bond. For some of them, the obtained dependences are far from self-evident.