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American Physical Society, Physical review B, 14(92)

DOI: 10.1103/physrevb.92.144107

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Ab initioperspective on the Mollwo-Ivey relation forFcenters in alkali halides

This paper is available in a repository.
This paper is available in a repository.

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Data provided by SHERPA/RoMEO

Abstract

We revisit the well-known Mollwo-Ivey relation that describes the "universal" dependence of the absorption energies of F-type color centers on the lattice constant $a$ of the alkali-halide crystals, $E_{\mbox{abs}}∝ a^{-n}.$ We perform both state-of-the-art ab-initio Quantum Chemistry and post-DFT calculations of F-center absorption spectra. By "tuning" independently the lattice constant and the atomic species we show that the scaling of the lattice constant alone (keeping the elements fixed) would yield $n=2$ in agreement with the "particle-in-the-box" model. Keeping the lattice constant fixed and changing the atomic species enables us to quantify the ion-size effects which are shown to be responsible for the exponent $n ≈ 1.8$.