In this work, we explore how the presence of a PD dictates the initial stages of nitride formation for LiMEAS. Using density functional theory (DFT) calculations, we show that in the absence of the PD, nitrogen does not spontaneously dissociate into a nitride, and nitrogen configurations on lithium show negligible bond elongation. For comparison, we investigate the energetics of nitrogen adsorption on a lithium slab, in the presence of 30 PDs that span the KT parameter space. By introducing a PD into the system, we observe new resulting nitrogen configurations with larger bond stretching. We categorize these recurring nitrogen configurations into 5 different states. These configurations exhibit thermodynamically favorable N 2 -lithium adsorption energy over accessible states without PDs. Probing these states further, we perform a charge analysis and highlight correlations between charge transfer and nitrogen bond length. This analysis stresses the involved role of the PD in driving nitride formation.