Hydrogen Bond Blueshifts in Nitrile Vibrational Spectra Are Dictated by Hydrogen Bond Geometry and Dynamics.

ABSTRACT: Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine the strength of noncovalent, electrostatic interactions in chemistry and biology and to quantify their influence on structure and reactivity. Nitriles (C≡N) have been widely used as VSE probes, but their application has been complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within the VSE framework. We present an empirical model describing the anomalous HB blueshift in terms of H-bonding geometry, i.e., as a function of HB distance and angle with respect to the C≡N group. This model is obtained by comparing vibrational observables from density functional theory and electrostatics from the polarizable AMOEBA force field, and it provides a phys

SUBMITTER: Kirsh JM 

PROVIDER: S-EPMC11672138 | biostudies-literature | 2024 Dec

REPOSITORIES: biostudies-literature