While it is accepted that the plastic behavior of metallic glasses is affected by their free volume content, the effect on chemical bonding has not been investigated systematically. According to electronic structure analysis, the overall bond strength is not significantly affected by the free volume content. However, with an increasing free volume content, the average coordination number decreases. Furthermore, the volume fraction of regions containing atoms with a lower coordination number increases. As the local bonding character changes from bonding to anti-bonding with a decreasing coordination number, bonding is weakened in the volume fraction of a lower coordination number. During deformation, the number of strong, short-distance bonds decreases more for free volume-containing samples than for samples without free volume, resulting in additional bond weakening. Therefore, we show that the introduction of free volume causes the formation of volume fractions of a lower coordination number, resulting in weaker bonding, and propose that this is the electronic structure origin of the enhanced plastic behavior reported for glasses containing free volume.
Keywords: ab initio; electronic structure; free volume; metallic glass.