Kinetic pathways of coesite densification from metadynamics

TL;DR

This study uses advanced computational methods to elucidate the atomic mechanisms of coesite's transformation into denser phases under high pressure, matching experimental observations and predicting temperature-dependent pathways.

Contribution

It introduces a novel metadynamics approach combined with machine-learning potentials to simulate complex phase transformations in coesite at the atomic level.

Findings

Pathways to coesite-IV and octahedral phases are identified and characterized.

Transformation mechanisms depend on temperature, favoring different pathways.

Computational results align with experimental phase observations.

Abstract

We study compression of coesite to pressures above 35 GPa, substantially beyond the equilibrium transition pressure to octahedral phases (8 GPa to stishovite). Experiments at room temperature showed that up to 30 GPa the metastable coesite structure develops only minor displacive changes (coesite-II and coesite-III) while the Si atoms remain 4-coordinated. Beyond 30 GPa, reconstructive transformations start, following different pathways from the complex structure of coesite. Besides amorphization, two different crystalline outcomes were observed. One is formation of defective high-pressure octahedral phases (Hu et al., 2015) and another one is formation of unusual and complex dense phases coesite-IV and coesite-V with Si atoms in 4-fold, 5-fold and 6-fold coordination (Bykova et al., 2018). Capturing these structural transformations computationally represents a challenge. Here we show that employing metadynamics with Si-O coordination number and volume as generic collective variables in combination with a machine-learning based ACE potential (Erhard et al., 2024), one naturally observes all three mentioned pathways, resulting in the phases observed experimentally. We describe the atomistic mechanisms along the transformation pathways. While the pathway to coesite-IV is simpler, the transformation to octahedral phases involves two steps: first, a hcp sublattice of O atoms is formed where Si atoms occupy octahedral positions but the octahedra chains do not form a regular pattern. In the second step, the Si atoms order and the chains develop a more regular arrangement. We predict that the pathway to coesite-IV is preferred at room temperature, while at 600 K the formation of octahedral phases is more likely.