Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system

• Raman and IR spectra of multiferroic [(CH3)2NH2][Ni(HCOO)3] were recorded.
• DFT calculations for the model compounds were performed.
• Assignment of vibrational modes has been proposed.
• Modes sensitive to formation of hydrogen bonds have been identified.

Experimental Raman and IR spectra of multiferroic [(CH3)2NH2][Ni(HCOO)3] were recorded at room temperature. The three-parameter hybrid B3LYP density functional method has been used with the 6-31G(d, p) basis set to derive the equilibrium geometry, atomic spin densities, vibrational wavenumbers, infrared intensities and Raman scattering activities. Based on these calculations, the assignment of the observed bands to the respective internal and lattice modes is proposed. The performed calculations revealed that the ν(NH2) stretching, ρ(NH2) rocking and τ(CH3) torsional modes are very sensitive to formation of the hydrogen bond between the DMA+ cation and Ni-formate framework. Therefore, these modes are suitable probes for strength of hydrogen bonds in this family of metal-formate frameworks and study of their temperature dependence may provide significant information on a role of the hydrogen bonds in mechanism of the ferroelectric phase transition occurring in these compounds at low temperatures.

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