Mott-Hubbard versus charge-transfer behavior in LaSrMnO4 studied via optical conductivity

TL;DR

This study uses optical spectroscopy and multiplet calculations to analyze the electronic structure and temperature-dependent optical properties of LaSrMnO4, revealing its Mott-Hubbard insulating behavior and anisotropic optical responses.

Contribution

The paper provides a detailed multiplet-based analysis of LaSrMnO4's optical conductivity, assigning peaks to electronic transitions and determining key electronic parameters, confirming its Mott-Hubbard insulator nature.

Findings

Effective parameters: U_eff=2.2 eV, Delta_a=4.5 eV.

Spectral weight of low-energy absorption doubles across Neel temperature.

Anisotropic optical gap values at different temperatures.

Abstract

Using spectroscopic ellipsometry, we study the optical conductivity sigma(omega) of insulating LaSrMnO4 in the energy range of 0.75-5.8 eV from 15 to 330 K. The layered structure gives rise to a pronounced anisotropy. A multipeak structure is observed in sigma_1^a(omega) (2, 3.5, 4.5, 4.9, and 5.5 eV), while only one peak is present at 5.6 eV in sigma_1^c(omega). We employ a local multiplet calculation and obtain (i) an excellent description of the optical data, (ii) a detailed peak assignment in terms of the multiplet splitting of Mott-Hubbard and charge-transfer absorption bands, and (iii) effective parameters of the electronic structure, e.g., the on-site Coulomb repulsion U_eff=2.2 eV, the in-plane charge-transfer energy Delta_a=4.5 eV, and the crystal-field parameters for the d^4 configuration (10 Dq=1.2 eV, Delta_eg=1.4 eV, and Delta_t2g=0.2 eV). The spectral weight of the lowest absorption feature (at 1-2 eV) changes by a factor of 2 as a function of temperature, which can be attributed to the change of the nearest-neighbor spin-spin correlation function across the Neel temperature. Interpreting LaSrMnO4 effectively as a Mott-Hubbard insulator naturally explains this strong temperature dependence, the relative weight of the different absorption peaks, and the pronounced anisotropy. By means of transmittance measurements, we determine the onset of the optical gap Delta^a_opt=0.4-0.45 eV at 15 K and 0.1-0.2 eV at 300 K. Our data show that the crystal-field splitting is too large to explain the anomalous temperature dependence of the c-axis lattice parameter by thermal occupation of excited crystal-field levels. Alternatively, we propose that a thermal population of the upper Hubbard band gives rise to the shrinkage of the c-axis lattice parameter.