To elucidate the atomistic origin of volume relaxation in soda-lime silicate glass annealed below the glass transition temperature (Tg), the experimental and calculated Raman spectra were compared. By decomposing the calculated Raman spectra into specific groups of atoms, the Raman peaks at 800, 950, 1050, 1100, and 1150 cm−1 were attributed to oxygen and silicon in Si–O–Si, non-bridging oxygen in the Q2 unit, bridging oxygen in low-angle Si–O–Si, non-bridging oxygen in the Q4 unit, and bridging oxygen in high-angle Si–O–Si, respectively. Based on these attributions, we found that by decreasing the fictive temperature by annealing below Tg − 70 K, a homogenization reaction Q2 + Q4 → 2Q3 and an increase in average Si–O–Si angle occurred simultaneously. By molecular dynamics simulation, we clarified how the experimentally demonstrated increase in average Si–O–Si angle contributes to volume shrinkage; increasing Si–O–Si angles can expand the space inside the rings, and Na can be inserted into the ring center.

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