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On the basis of ab initio molecular dynamics modeling, we show that Ge-Sb-Te alloy under excitation can realize amorphization without going through a liquid phase. The electronic structure analysis further reveals that the excitation mainly involves the Ge s-like states near the valence band maximum. After the phase transition, the coordination number of Ge is reduced from six to four, while the change in the coordination number for Sb is noticeably less.