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First-principles study of intrinsic and Fe3+-related luminescence mechanisms in feldspar

Mingxue Fu1,*, Arghya Bhowmik1,†, Mayank Jain2,‡, and Juan Maria Lastra-García1,§

  • *Contact author: mifuaa@dtu.dk
  • †Contact author: arbh@dtu.dk
  • ‡Contact author: maja@dtu.dk
  • §Contact author: jmgla@dtu.dk
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Phys. Rev. B 113, 134107 – Published 9 April, 2026

DOI: https://doi.org/10.1103/597n-n66p

Abstract

Feldspar is the most abundant mineral group in the Earth's continental crust and almost invariably contains Fe3+ impurities in natural samples. These impurities dominate the characteristic deep-red luminescence of feldspar, while the host lattice itself also exhibits intrinsic luminescence associated with self-trapped excitons (STEs). Despite the central role of feldspar in luminescence dosimetry and geochronology, the microscopic mechanisms underlying both intrinsic and Fe3+-related luminescence remain incompletely understood. Here, we present a comprehensive first-principles investigation of disorder, intrinsic defects, and impurity-related charge trapping in K-feldspar. Using a cluster expansion trained on density functional theory calculations, we determine the ground-state Al–Si ordering and quantify the formation of Al–O–Al linkages at high temperatures. Based on this structure, we identify energetically favorable intrinsic defects and demonstrate that hole polarons localize preferentially on oxygen atoms bridging AlO4 and SiO4 tetrahedra, while Si–O–Si bridges do not stabilize holes. Rare Al–O–Al bridges formed at melting temperatures are shown to be particularly efficient hole traps. We compute STE configurations and vertical emission energies using a hybrid functional approach, obtaining emission energies in excellent agreement with experimental measurements. Furthermore, we show that Fe3+ impurities strongly modify local charge trapping: Fe3+ preferentially captures electrons to form Fe2+, while also stabilizing hole polarons on neighboring oxygen sites, forming metal-oxyl complexes. Based on these results, we propose a microscopic mechanism for Fe3+-related luminescence in which electron capture by Fe3+ is followed by spin-selective recombination that populates the Fe3+ excited state T14. Our results provide a unified atomistic picture of intrinsic and impurity-driven luminescence in feldspar and establish a quantitative foundation for modeling charge trapping and recombination processes relevant to luminescence dating.

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Phys. Rev. B 113, 134107– Published 9 April, 2026
  • Received 11 February 2026
  • Accepted 16 March 2026
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