Yttrium alumino-silicate (YAS) glass has an application in in situ cancer radiotherapy. [1] Conventional radiotherapy irradiates a tumor from a radiation source external to the body, which can cause substantial damage to the surrounding healthy tissue. On the other hand, internal, or in situ, radiotherapy implants a radiation source into the tumor or surrounding blood vessels, from where it can irradiate the tumor directly. This approach reduces the unnecessary damage to healthy tissues and the corresponding side effects of conventional radiotherapy. One method currently used for in situ radiotherapy is to inject a solution of YAS glass microspheres, in which the 90 Y isotope has been excited to a radioactive state, into the blood vessels supplying the tumor.The microspheres then reach and settle in the target tumor, which is hit by the localized radiation released from the yttrium source bound within the glass. The in situ method has been successful in treating deeply seated tumors associated with liver and kidney cancer, which are difficult to treat with conventional radiotherapy. [2,3] The key property of the glass for the success of this application is its chemical durability, defined as the inverse of the release rate of yttrium in the physiological environment. The glass should release as little radioactive 90 Y into the bloodstream as possible, because any yttrium so released would be transported to other healthy organs, which would be exposed to harmful doses of radiation. The half-life of 90 Y is 2.7 days, so the microspheres need only to be durable over a timescale of a few weeks. Several compositions of YAS glass were tested experimentally, and that with the highest durability, commonly used in in situ radiotherapy, had 17.1 mol% Y 2 O 3 , 18.9 mol% Al 2 O 3 , and 64.0 mol% SiO 2 (this composition is hereafter termed YAS17). [4] In order to optimize this kind of cancer treatment, it is critical to understand how yttrium is bound into the glass network and the factors which control its dissolution from the bulk glass into a surrounding fluid; however, the atomistic properties of YAS glass, particularly those relating to the local yttrium structure, are not well understood. There is only a We present Car-Parrinello molecular dynamics (CPMD) simulations of yttrium alumino-silicate (YAS) glass. Alumino-silicate glass microspheres are used as vectors of yttrium radioisotopes in cancer radiotherapy; understanding in detail how yttrium is bound within the glass network is important to control the unwanted release of radioactive yttrium in the bloodstream. Our simulations, focused on a specific composition relevant to practical applications, show that silicon and aluminum form a disordered glass network, where Si is mainly four-coordinated, whereas, Al is mainly four-and five-coordinated. Yttrium cations have a network-modifying role, disrupting the alumino-silicate network by breaking Si(Al)ÀO bonds and coordinating the resulting non-bridging oxygens (NBO). The local environment of yttrium in the glass turns ...