glass is treated as a molecule. The potential for P-S bonds and S-P-S angles within the PS 4 3unit is represented by polynomial functions for bond distance and angle, enabling annealing at high temperatures while preserving the PS 4 3units. This approach results in a realistic glass structure upon quenching, as validated by agreement with diffraction data. The COMPASS force field has been extensively validated for sulfide-based solid electrolytes and accurately reproduces experimental observations of structural factors and Li + diffusion. Thermal analysis and 31 P solid-state NMR studies demonstrate that no P-S bond cleavage or formation occurs during crystallization. CMD with this molecular force field is, therefore, a reliable method for this study.