First-principles molecular dynamics based on density functional theory (DFT-MD) is an approach that can be used to overcome the limitations of CMD. DFT-MD can be used to simulate multicomponent systems without dependence on the potential parameters. In fact, the presence of boroxol rings and boron superstructures in borosilicate glasses can be reproduced in glass structures obtained by DFT-MD simulations. If a reliable CMD potential is not available for the glass of interest, DFT-MD is the preferred choice. However, with this approach, the system size is limited owing to high computational cost; for instance, the structures of elements present in small amounts in the glasses cannot be analyzed with high statistical precision in calculations with hundreds of atoms.