Spin-forbidden excitations in the magneto-optical spectra of CrI$_3$ tuned by covalency

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Main Authors: Occhialini, Connor A., Nessi, Luca, Martins, Luiz G. P., Demir, Ahmet Kemal, Song, Qian, Hasse, Vicky, Shekhar, Chandra, Felser, Claudia, Watanabe, Kenji, Taniguchi, Takashi, Bisogni, Valentina, Pelliciari, Jonathan, Comin, Riccardo
Format: Preprint
Published: 2025
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author Occhialini, Connor A.
Nessi, Luca
Martins, Luiz G. P.
Demir, Ahmet Kemal
Song, Qian
Hasse, Vicky
Shekhar, Chandra
Felser, Claudia
Watanabe, Kenji
Taniguchi, Takashi
Bisogni, Valentina
Pelliciari, Jonathan
Comin, Riccardo
author_facet Occhialini, Connor A.
Nessi, Luca
Martins, Luiz G. P.
Demir, Ahmet Kemal
Song, Qian
Hasse, Vicky
Shekhar, Chandra
Felser, Claudia
Watanabe, Kenji
Taniguchi, Takashi
Bisogni, Valentina
Pelliciari, Jonathan
Comin, Riccardo
contents Spin-forbidden ($ΔS \neq 0$) multiplet excitations and their coupling to magnetic properties are of increasing importance for magneto-optical studies of correlated materials. Nonetheless, the mechanisms for optically brightening these transitions and their generality remain poorly understood. Here, we report magnetic circular dichroism (MCD) spectroscopy on the van der Waals (vdW) ferromagnet (FM) CrI$_3$. Previously unreported spin-forbidden ($ΔS = 1$) ${}^4A_{2\mathrm{g}} \to{}^2E_\mathrm{g}/{}^2T_{1\mathrm{g}}$ Cr${}^{3+}$ $dd$ excitations are observed near the ligand-to-metal charge transfer (LMCT) excitation threshold. The assignment of these excitations and their Cr$^{3+}$ multiplet character is established through complementary Cr $L_3$-edge resonant inelastic X-ray scattering (RIXS) measurements along with charge transfer multiplet (CTM) calculations and chemical trends in the chromium trihalide series (CrX$_3$, X = Cl, Br, I). We utilize the high sensitivity of MCD spectroscopy to study the thickness dependent optical response. The spin-forbidden excitations remain robust down to the monolayer limit and exhibit a significant magnetic field tunability across the antiferromagnetic to FM transition in few-layer samples. This behavior is associated to changes in the metal-ligand covalency with magnetic state, as supported by our CTM analysis. Our results clarify the magneto-optical response of CrI$_3$ and identify covalency as a central mechanism for the brightening and field-tunability of spin-forbidden multiplet excitations.
format Preprint
id arxiv_https___arxiv_org_abs_2501_17417
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Spin-forbidden excitations in the magneto-optical spectra of CrI$_3$ tuned by covalency
Occhialini, Connor A.
Nessi, Luca
Martins, Luiz G. P.
Demir, Ahmet Kemal
Song, Qian
Hasse, Vicky
Shekhar, Chandra
Felser, Claudia
Watanabe, Kenji
Taniguchi, Takashi
Bisogni, Valentina
Pelliciari, Jonathan
Comin, Riccardo
Strongly Correlated Electrons
Mesoscale and Nanoscale Physics
Spin-forbidden ($ΔS \neq 0$) multiplet excitations and their coupling to magnetic properties are of increasing importance for magneto-optical studies of correlated materials. Nonetheless, the mechanisms for optically brightening these transitions and their generality remain poorly understood. Here, we report magnetic circular dichroism (MCD) spectroscopy on the van der Waals (vdW) ferromagnet (FM) CrI$_3$. Previously unreported spin-forbidden ($ΔS = 1$) ${}^4A_{2\mathrm{g}} \to{}^2E_\mathrm{g}/{}^2T_{1\mathrm{g}}$ Cr${}^{3+}$ $dd$ excitations are observed near the ligand-to-metal charge transfer (LMCT) excitation threshold. The assignment of these excitations and their Cr$^{3+}$ multiplet character is established through complementary Cr $L_3$-edge resonant inelastic X-ray scattering (RIXS) measurements along with charge transfer multiplet (CTM) calculations and chemical trends in the chromium trihalide series (CrX$_3$, X = Cl, Br, I). We utilize the high sensitivity of MCD spectroscopy to study the thickness dependent optical response. The spin-forbidden excitations remain robust down to the monolayer limit and exhibit a significant magnetic field tunability across the antiferromagnetic to FM transition in few-layer samples. This behavior is associated to changes in the metal-ligand covalency with magnetic state, as supported by our CTM analysis. Our results clarify the magneto-optical response of CrI$_3$ and identify covalency as a central mechanism for the brightening and field-tunability of spin-forbidden multiplet excitations.
title Spin-forbidden excitations in the magneto-optical spectra of CrI$_3$ tuned by covalency
topic Strongly Correlated Electrons
Mesoscale and Nanoscale Physics
url https://arxiv.org/abs/2501.17417