A mode-coupling theory analysis of the rotation driven translational motion of aqueous polyatomic ions

TL;DR

This paper uses mode-coupling theory to explain the anomalous diffusion behavior of complex polyatomic ions in water, highlighting the role of rotational jumps in their translational motion.

Contribution

It introduces a mode-coupling theory framework that incorporates rotational jumps to interpret the diffusion anomalies of polyatomic ions in aqueous solutions.

Findings

Mode-coupling theory successfully explains diffusion differences.

Rotational jumps significantly influence translational friction.

Theoretical predictions agree with experimental and simulation data.

Abstract

In contrast to simple monatomic alkali and halide ions, complex polyatomic ions like nitrate, acetate, nitrite, chlorate etc. have not been studied in any great detail. Experiments have shown that diffusion of polyatomic ions exhibits many remarkable anomalies, notable among them is the fact that polyatomic ions with similar size show large difference in their diffusivity values. This fact has drawn relatively little interest in scientific discussions. We show here that a mode-coupling theory (MCT) can provide a physically meaningful interpretation of the anomalous diffusivity of polyatomic ions in water, by including the contribution of rotational jumps on translational friction. The two systems discussed here, namely aqueous nitrate ion and aqueous acetate ion, although have similar ionic radii exhibit largely different diffusivity values due to the differences in the rate of their rotational jump motions. We have further verified the mode-coupling theory formalism by comparing it with experimental and simulation results that agrees well with the theoretical prediction.