The influence of cations on the dipole moments of neighboring polar molecules

TL;DR

This paper investigates how cations influence the dipole moments of neighboring polar molecules, revealing that polarization effects are primarily due to electrostatic charge, with molecular arrangements affecting overall dipole behavior.

Contribution

It introduces a detailed analysis of cation-induced polarization effects on polar molecules, considering both electrostatic and electron donation influences.

Findings

Cations increase neighboring molecules' dipole moments mainly through electrostatic polarization.

Molecular arrangements in the first solvation shell can reduce individual dipole moments.

Some molecules exhibit dipole moments smaller than their free forms due to mutual polarization.

Abstract

It is shown that the dipole moment of polar (water, methanol, formamide, acetone and acetonitrile) molecules in the neighborhood of a cation is increased primarily by polarization from the bare electrostatic charge of the cation, although the effective value of the latter is somewhat reduced by "back donation" of electrons from neighbouring polar molecules. In other words, the classical picture may be viewed as if a point charge slightly smaller than the nominal charge of the cation would be placed at the cation site. It was found that the geometrical arrangement of the polar molecules in the first solvation shell is such that their mutual polarization reduces the dipole moments of individual molecules, so that in some cases they become smaller than the dipole moment of the free protic or aprotic molecule. We conjecture that this behavior is essentially a manifestation of the Le Chatellier-Braun principle.