AbstractTheoretical prediction of glass compositions with certain performance requirements is a long‐standing challenge in glass research. The difficulty lies in revealing the relationship of glass's composition–structure–property (C–S–P), and establishing a predictive calculation method for glass properties with high accuracy. Here we determine quantitatively the C–S–P relationships of four silicate laser glasses using nearest‐neighboring congruently melting compounds (CMCs) as “component and structural motifs”. For all studied silicate systems, physical properties such as density and refractive index are predicted with an error of less than 5%. Spectroscopic properties, including Judd–Ofelt parameters, fluorescence branching ratio (β), effective bandwidth (Δλeff), emission cross‐section (σe), gain bandwidth, and lifetime, are predicted with an error of less than 10%, with some properties such as β, Δλeff, and σe showing an error of less than 5% in specific systems. Four C–S–P databases have also been constructed, containing detailed physical and spectroscopic properties of over 1200 compositions, facilitating the optimization of glass composition. These findings highlight the significance of nearest‐neighboring CMCs in understanding and developing high‐performance laser glasses.
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