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Local distortions and B-site-resolved environments in Ca2Mn1−xTixO4 solid solutions

A. Neves Cesário1, S. S. M. Santos2,3, P. Rocha-Rodrigues1, P. Neenu Lekshmi1, P. S. Sousa1, J. G. Correia4, J. P. Araújo1, L. V. C. Assali2, H. M. Petrilli2 et al.

M. S. Senn5 and A. M. L. Lopes1,*

  • *Contact author: armandina.lima.lopes@cern.ch
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Phys. Rev. B 114, 144101 – Published 2 September, 2026

DOI: https://doi.org/10.1103/b18r-2d5k

Abstract

A series of Ruddlesden-Popper perovskite solid solutions, Ca2Mn1−xTixO4 (0.25≤x≤0.65), is examined by combining density functional theory (DFT) calculations with local-scale experimental studies conducted at ISOLDE-CERN over a broad temperature range (10–1220 K). Perturbed angular correlation (PAC) spectroscopy probes the I4/mmm to I41/acd structural phase transitions for all compositions between 900 and 1200 K. For x=0.65, measurements below 160 K show that a second structural phase condenses, coexisting with the I41/acd phase down to 10 K. DFT structural models reproduce a key experimental observation: in the I41/acd phase, the c lattice parameter shows only a minor increase upon Ti substitution, whereas the ab plane expands significantly, reducing the c/a ratio linearly. This anisotropic response can be attributed to a corkscrewlike mechanism, where the enhancement of in-plane BO6 octahedral rotations induces a contraction of the rocksalt layers, thereby mitigating the expansion of the c axis. PAC data, supported by DFT calculations, demonstrate that Ca sites apically connected to MnO6 octahedra exhibit experimentally distinguishable Electric Field Gradients from those connected to TiO6 octahedra.

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Phys. Rev. B 114, 144101– Published 2 September, 2026
  • Received 6 February 2026
  • Revised 15 May 2026
  • Accepted 16 June 2026
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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