Ab initio studies for characterization and identification of nanocrystalline copper pyrophosphate confined in mesoporous silica

Here we employ a novel method for preparing the homogeneous copper pyrophosphate nanocrystals inside silica mesopores. In order to characterize and identify synthesized nanocrystals we performed theab initiostudies of theαphase of Cu₂P₂O₇. The electronic and crystal structure were optimized within the density functional theory with the strong electron interactions in the3dstates on copper atoms and van der Waals corrections included in calculations. The relaxed lattice parameters and atomic positions agree very well with the results of the diffraction measurements for nanocrystalline copper pyrophosphates embedded inside SBA-15 silica pores. The obtained Mott insulating state with the energy gap of 3.17 eV exhibits the antiferromagnetic order with magnetic moments on copper atoms (0.8μB) that is compatible with the experimental studies. The phonon dispersion relations were obtained to study the dynamical properties of the Cu₂P₂O₇lattice and the element-specific atomic vibrations were analyzed using the partial phonon density of states. The calculated Raman spectrum revealed the consistency of typical bands of Cu₂P₂O₇with the experimental data. The investigation that combines a new synthesis of nanomaterials with the first-principles calculations is important for better characterization and understanding of the physical properties relevant for nanotechnological applications.