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Vibrational and reorientational motions of H2O ligands, phase transition and thermal properties of [Sr(H2O)6]Cl2. | LitMetric
One phase transition (PT) at TC(h)=252.9K (on heating) and at TC(c)=226.5K (on cooling) was detected by DSC for [Sr(H2O)6]Cl2 in 123-295K range. Thermal hysteresis of this PT equals to 26.4K. Entropy change (ΔS) value at this first-order type phase transition equals to ca. 1.5Jmol(-1)K(-1). The temperature dependences of the full width at half maximum (FWHM) values of the infrared bands associated with ρt(H2O)E and δas(HOH)E modes (at ca. 417 and 1628cm(-1), respectively) suggest that the observed phase transition is associated with a sudden change of a speed of the H2O reorientational motions. The H2O ligands in the high temperature phase reorientate quickly (correlation times 10(-11)-10(-13)s) with the activation energy of ca. 2kJmol(-1). Below TC(c) probably a part of the H2O ligands stop their reorientation, while the remainders continue their fast reorientation but with the activation energy of ca. 8kJmol(-1). Far and middle infrared spectra indicated characteristic changes at the vicinity of PT with decreasing of temperature, which suggested lowering of the crystal structure symmetry. Splitting of the band (at 3601cm(-1)) connected with vas(OH) mode near the TC(c) suggests lowering of the crystal lattice symmetry. All these facts suggest that the discovered PT is connected both with a change of the reorientational dynamics of the H2O ligands and with the change of the crystal structure.
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