Mechanical versus thermal amorphization of ZIF-4: from local rearrangements to network disorder

Abstract

There is mounting evidence that different amorphization routes can produce metalorganic framework (MOF) glasses with distinct structures and properties, yet the microscopic origins of these differences remain difficult to establish experimentally. Focusing on the two main synthesis methods, which are melt-quenching and ball-milling, we use molecular dynamics simulations with a machine-learning interatomic potential to compare different glasses obtained from ZIF-4. While both routes largely preserve tetrahedral zinc coordination, mechanical deformation generally produces more distorted local environments, showing that average coordination numbers alone do not capture the structural differences between these glasses. At smaller applied strain, mechanical glasses retain substantial memory of the crystalline network topology, despite pronounced changes in ring geometry. Larger strains erase this topological memory, yielding ring-size distributions similar to those of melt-quenched glasses, while differences in local geometry and porosity persist. Simulations of larger systems reveal a heterogeneous amorphization mechanism, involving the formation and growth of disordered domains. These findings from in silico amorphization support process-dependent polyamorphism in ZIF glasses and identify local geometry, topological memory, and spatial heterogeneity as complementary features needed to characterize their structure and understand the influence of mechanical processing.

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BibTeX RIS

BibTeX

@misc{triestram2026mechanical,
  title = {{Mechanical versus thermal amorphization of ZIF-4: from local rearrangements to network disorder}},
  author = {Léna Triestram and François-Xavier Coudert},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010773/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010773/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Mechanical versus thermal amorphization of ZIF-4: from local rearrangements to network disorder
AU  - Léna Triestram
AU  - François-Xavier Coudert
PY  - 2026
DA  - 2026/10/21
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010773/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010773/v1
AB  - There is mounting evidence that different amorphization routes can produce metalorganic framework (MOF) glasses with distinct structures and properties, yet the microscopic origins of these differences remain difficult to establish experimentally. Focusing on the two main synthesis methods, which are melt-quenching and ball-milling, we use molecular dynamics simulations with a machine-learning interatomic potential to compare different glasses obtained from ZIF-4. While both routes largely preserve tetrahedral zinc coordination, mechanical deformation generally produces more distorted local environments, showing that average coordination numbers alone do not capture the structural differences between these glasses. At smaller applied strain, mechanical glasses retain substantial memory of the crystalline network topology, despite pronounced changes in ring geometry. Larger strains erase this topological memory, yielding ring-size distributions similar to those of melt-quenched glasses, while differences in local geometry and porosity persist. Simulations of larger systems reveal a heterogeneous amorphization mechanism, involving the formation and growth of disordered domains. These findings from in silico amorphization support process-dependent polyamorphism in ZIF glasses and identify local geometry, topological memory, and spatial heterogeneity as complementary features needed to characterize their structure and understand the influence of mechanical processing.
ER  -

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