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Structural Transformation Behind the Deep Eutectic Phenomenon in the Au-Si System.

Xue Zhang1,2, Dianjin Xi1,2, Hailong Wang1,2

  • 1University of Science and Technology of China, Hefei 230026, China.

Inorganic Chemistry
|February 20, 2026
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The deep eutectic phenomenon in gold-silicon (Au-Si) systems is explained by the formation of metastable Au4Si crystals. DFT calculations reveal weaker Au-Au and Au-Si bonds due to electron transfer, facilitating melting.

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Area of Science:

  • Materials Science
  • Computational Materials Science
  • Solid State Chemistry

Background:

  • The deep eutectic phenomenon in the gold-silicon (Au-Si) system is a long-standing puzzle.
  • Understanding its structural origin is crucial for both fundamental science and practical applications.

Purpose of the Study:

  • To investigate the structural basis of the deep eutectic phenomenon in the Au-Si system.
  • To elucidate the atomic-level mechanisms driving the formation and melting of metastable phases.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed.
  • Phonon density of states (PDOS), energy analysis, Crystal Orbital Hamilton Population (COHP), and Hirshfeld population analyses were performed.

Main Results:

  • DFT confirms energetically favorable silicon (Si) diffusion into the gold (Au) lattice, forming metastable Au4Si crystals.
  • A body-centered cubic (bcc) Au4Si structure was identified as key to eutectic behavior, with weaker Au-Au and Au-Si bonds.
  • Valence electron transfer from Au to Si and intensified atomic vibrations at elevated temperatures weaken bonds and promote melting.

Conclusions:

  • The study provides a structural and bonding-based explanation for the deep eutectic behavior in the Au-Si system.
  • Metastable bcc-Au4Si formation and subsequent bond weakening are identified as the primary drivers of the phenomenon.