Resolving Lonsdaleite's decade-long controversy: Atomistic insights into a metastable diamond polymorph

Abstract

Lonsdaleite, a theoretically proposed hexagonal diamond polymorph, has remained at the center of a five-decade scientific controversy since its 1967 identification. While some studies claim it exhibits superior hardness through compression-induced structural changes, others contend it is merely a stacking-faulted cubic diamond. Meteoritic samples and synthetic preparations have yielded conflicting evidence, with even advanced characterisation techniques like XRD and TEM failing to provide definitive proof. In this work, we employ first-principles density functional theory (DFT) and molecular dynamics (MD) simulations to generate unambiguous theoretical fingerprints through XRD, Raman, and SAED patterns that distinguish true Lonsdaleite from cubic diamond and its defective variants. Our atomistic approach quantifies the thermodynamic metastability of Lonsdaleite under realistic pressure-temperature conditions, reveals distinct spectral signatures through simulated Raman and resolves the structural ambiguity through generalised stacking fault energy analysis. By establishing clear criteria for definitive identification, this study provides long-awaited clarity to the Lonsdaleite debate while offering a robust computational framework for characterising metastable carbon phases in meteoritic, synthetic and industrial materials.