The contribution of nitrogen Frenkel-pair formation to the high-temperature heat capacity of uranium mononitride

TL;DR

This study uses molecular dynamics simulations to investigate how nitrogen Frenkel-pair formation influences the high-temperature heat capacity of uranium mononitride, revealing defect contributions that explain observed superlinear behavior.

Contribution

It provides the first large-scale MD simulation analysis of nitrogen defect formation in UN at high temperatures, linking defect populations to heat capacity.

Findings

Frenkel-pair concentrations increase with temperature

Defect heat capacity contribution up to ~10 J/(mol-K)

Nitrogen sublattice disorder explains high-temperature heat capacity behavior

Abstract

The high-temperature heat capacity of uranium mononitride (UN) remains uncertain due to conflicting measurements and models above ~1700 K. To assess whether intrinsic defect formation contributes to the observed superlinear behavior of $C_P(T)$, we perform large-scale molecular dynamics simulations using two interatomic potentials to quantify nitrogen diffusion and Frenkel-pair populations from 1800--2600 K. Both models show increasing anion mobility, but the Tseplyaev potential yields substantially larger Frenkel concentrations, producing a defect heat-capacity contribution of up to ~10 J/(mol-K). This defect-driven term is consistent with the curvature seen in historical correlations and recent ab initio results, suggesting that nitrogen sublattice disorder provides a plausible intrinsic mechanism for the high-temperature heat capacity of UN.