Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system.
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.
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2, Poland. Electronic address: m.maczka@int.pan.wroc.pl.
M
M
Mączka
Faculty of Chemistry, Wrocław University of Technology, ul. Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
W
W
Zierkiewicz
Faculty of Chemistry, Wrocław University of Technology, ul. Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
D
D
Michalska
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2, Poland; Department of Bioorganic Chemistry, Faculty of Industry and Economics, Wrocław University of Economics, 118/120 Komandorska Str., 53-345 Wrocław, Poland.
J
J
Hanuza
D017610:Calcium Compounds / Q000737:chemistry*; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D014025:Titanium / Q000737:chemistry*
D017610:Calcium Compounds; D010087:Oxides; C059910:perovskite; D009532:Nickel; D014025:Titanium
DFT; Formates; IR spectra; Metal–organic frameworks; Raman spectra