Work

Partial atomic charge of oxygen and hydrogen-bonding ability: insights from mass-selective IR spectroscopy of jet-cooled hydrogen-bonded complexes

Year: 2025

Type: article

Abstract: ) serves as a direct measure of hydrogen-bond strength. We analysed two series of acceptors, acyclic alcohols and ethers, which demonstrate increasing inductive effects, and cyclic ethers, which reveal the influence of resonance. The gas-phase spectroscopy results provide a dataset that serves as a benchmark for validating computational chemistry models used for atomic charge calculation. It was demonstrated that while standard hydrogen-bonding descriptors correlate well with the experimental data, many popular partial atomic charge models fail to reproduce the observed chemical trends. This failure could be due to the over-reliance of the models on the electronegativity of directly bonded atoms. By highlighting this discrepancy, this work serves as a valuable cautionary example regarding the use of atomic charges and underscores the need for better theoretical frameworks for atomic charge estimation.

Source: Physical Chemistry Chemical Physics

DOI: 10.1039/d5cp03250d

Authors: Akshay Kumar Sahu, Anant Ram Satpathi, Saiprakash Rout, Radharaman Samanta, Laxmipriya Dash, Himansu S. Biswal

Institutions: National Institute of Science Education and Research, Homi Bhabha National Institute

Language: English

Topic: Molecular Spectroscopy and Structure

Subfield: Spectroscopy

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Funders: Arthritis National Research Foundation, National Research Foundation, Department of Atomic Energy, Government of India

Award: G3533059474