N(CH3)3H]2CuCl4: Ab initio calculations and characterization of phase transitions by Raman spectroscopy

Abstract

The X-ray powder diffraction pattern shows that at room temperature, [N(CH3)3H]2CuCl4is crystallized in the monoclinic system with P21/c space group. The phase transitions at T1 ≈ 292/298 K, T2 ≈ 262/264 K and T3 ≈ 241 Khave been confirmed by the differential scanning calorimetry (DSC). Besides, the different phases have been studied by Raman scattering on single crystals, in the frequency range of 60–350 cm−1. The infrared and Raman spectra are attributed on the basis of ab initio calculations of the vibrational spectra. The optimized geometries, calculated vibrational frequencies, infrared intensities and Raman activities of [CuCl4]2− and [N(CH3)3H]+were calculated using the Hartree-Fock (HF) and density functional theory (B3LYP) with 3-21G, 6-31G(d) and 6-311G(d,p)basis sets. The temperature evolution of Raman spectra reveals the existence of phase transitions at T1, T2 and T3 and confirms their nature.