This article discusses how x-irradiation affects the formation of silver clusters, based on spectroluminescent studies. Increasing the x-ray irradiation dose increases the optical density of the test glasses in the 300–450-nm region and causes an absorption band to appear in the 300-nm region in the case of glasses that contain Na<sup>+</sup>. Replacing Na<sup>+</sup> with Li<sup>+</sup> substantially increases the absorption in the 250–300-nm region, while replacing Na<sup>+</sup> with K<sup>+</sup> displaces the absorption band into the 313-nm region. Intense luminescence was observed in the 450–820-nm region in all the test glasses after x-irradiation. These results are explained by taking into account the change of the structure of the glass and the physicochemical properties when various alkali oxides are introduced. An analysis of the luminescence properties of the test glasses made it possible to assume that negatively charged clusters of silver and complexes of the form Ag<sub>n</sub>-Me were formed, where Me=Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>.
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