Molecular dynamics simulation of the order-disorder phase transition in solid NaNO$_2$

TL;DR

This study uses molecular dynamics simulations with a hybrid ab initio and electron gas approach to investigate the phase transition in solid NaNO$_2$, revealing ion rotation as the transition trigger and highlighting internal charge-transfer effects.

Contribution

It introduces a novel simulation method combining ab initio calculations with the Gordon-Kim electron gas theory to study phase transitions in NaNO$_2$.

Findings

Phase transition triggered by nitrite ion rotation.

Agreement with recent X-ray experimental results.

Identification of internal charge-transfer effects.

Abstract

We present molecular dynamics simulations of solid NaNO$_2$ using pair potentials with the rigid-ion model. The crystal potential surface is calculated by using an \emph{a priori} method which integrates the \emph{ab initio} calculations with the Gordon-Kim electron gas theory. This approach is carefully examined by using different population analysis methods and comparing the intermolecular interactions resulting from this approach with those from the \emph{ab initio} Hartree-Fock calculations. Our numerics shows that the ferroelectric-paraelectric phase transition in solid NaNO$_2$ is triggered by rotation of the nitrite ions around the crystallographical c axis, in agreement with recent X-ray experiments [Gohda \textit{et al.}, Phys. Rev. B \textbf{63}, 14101 (2000)]. The crystal-field effects on the nitrite ion are also addressed. Remarkable internal charge-transfer effect is found.