Abstract: | In this paper, the crystal structure, vacancy defect, local electron density and magnetic properties of Gd1-xCaxCrO3 (0 ≤ x ≤ 0.3) polycrystalline samples were investigated systematically. The crystal structural analyses show that all the samples are orthorhombic phase and a structural distortion happens around x = 0.3. Due to the formation of Cr4+ ions, both the lattice constant and the Cr–O bond length decrease. The results of positron annihilation spectrum reveals that the vacancy defect concentration increases and the local electron structure changes with the introduction of Ca2+ ions. The field-cooled (FC) and zero-field cooled (ZFC) curves of Gd1-xCaxCrO3 samples measured under H = 100 Oe exhibits negative magnetization characteristics due to the interaction between Gd3+ and Cr3+ ions, and the magnetism can be affected by the structural distortion. |