A distinct shift in the pair distribution function, as depicted in Fig. , indicated a phase transition. In the high-conductivity phase, a ring-like local density of Na + ions emerged, and their strong connectivity reflects long-range diffusion. The distribution of sulfur (S) atoms, as shown in Fig. , provided further evidence of PS 4 rotation. This rotational behavior was reaffirmed by the rapid decay of the angular autocorrelation function of PS 4 tetrahedra, as illustrated in Fig. . These findings collectively shed light on the intricate mechanisms governing the high ionic conductivity observed in the γ phase of Na 3 PS 4 .