Nature of the Frequency Shift of Hydrogen Valence Vibrations

TL;DR

This paper investigates the electrostatic origins of hydrogen vibrational frequency shifts in water, showing that intermolecular electrostatic forces primarily cause these shifts across various water states.

Contribution

It provides a theoretical calculation linking hydrogen vibrational frequency shifts to electrostatic interactions, supporting their dominant role in hydrogen bonding.

Findings

Frequency shifts are qualitatively consistent with experimental data.

Electrostatic forces are the main contributors to hydrogen bond effects.

Results apply across water vapor, ice, liquid water, and solutions.

Abstract

The physical nature of a frequency shift of hydrogen valence vibrations in a water molecule due to its interaction with neighbor molecules has been studied. Electrostatic forces connected with the multipole moments of molecules are supposed to give a dominating contribution to the intermolecular interaction. The frequency shift was calculated in the case where two neighbor molecules form a dimer. The obtained result is in qualitative agreement with the frequency shifts observed for water vapor, hexagonal ice, and liquid water, as well as for aqueous solutions of alcohols. This fact testifies to the electrostatic nature of H-bonds used to describe both the specific features of the intermolecular interaction in water and the macroscopic properties of the latter.