Phase transitions and H2O motions in [Ca(H2O)4](ClO4)2 studied by infrared spectroscopy, inelastic/quasielastic incoherent neutron scattering and proton magnetic resonance. Part II
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- 作者：Joanna Hetmań ; czyk ; Anna Migdał ; -Mikuli ; Edward Mikuli ; Krystyna Hoł ; derna-Natkaniec ; Ł ; ukasz Hetmań ; czyk ; Ireneusz Natkaniec
- 关键词：Tetraaquacalcium perchlorate ; Phase transitions ; Vibrational spectrum (FT-IR ; FT-RS) ; Molecular reorientations ; Inelastic and quasielastic incoherent neutron scattering (IINS and QENS) ; Proton magnetic resonance (1H NMR)
- 刊名：Journal of Molecular Structure
- 出版年：2009
- 出版时间：17 April 2009
- 年：2009
- 卷：923
- 期：1-3
- 页码：103-109
- 全文大小：592 K
文摘
Fourier transform middle infrared spectroscopy, inelastic/quasielastic incoherent neutron scattering and proton magnetic resonance data for [Ca(H2O)4](ClO4)2 in the temperature range of 20–300 K and 110–300 K, respectively, are reported. Lack of infrared bands broadening with increasing temperature indicated that molecular reorientational correlation time is longer than 10−12 s. The elastic peak of neutron inelastic scattering registered in the high temperature phase shows broadening, which can be well described by a model of 180° instantaneous stochastic jumps of protons around the two-fold axis formed by the CaO bond, assuming that only two out of four H2O ligands per [Ca(H2O)4]2+ formula unit undergoes fast reorientation with reorientational correlation time τR(H2O) of an order of 10−11 s. The analysis of the second moment M2 of 1H NMR line in the low temperature phase of [Ca(H2O)4](ClO4)2 revealed that the reorientation via 180° flips (jumps) of water molecules causes a very small changes of M2. It confirms that reorientation of H2O is fast even at 110 K. The reason for the first plateau of M2 ≈ 9.5 × 10−8 T2, which was observed at ca. 110–190 K range, is the anisotropic reorientation of whole [Ca(H2O)4]2+ cations around the two-fold symmetry axis going through two calcium atoms of the neighbouring [Ca(H2O)4]2+ cations. Above the phase transition at , the anisotropic reorientation of [Ca(H2O)4]2+ (around the pseudo three-fold symmetry axis formed by the Ca…O direction between [Ca(H2O)4]2+ cation and ClO4− anion, lying along the hydrogen bridge bond OH…O) is setting on with a frequency of the order of a few kHz, consequently above one can observe next plateau of M2 ≈ 2.5 × 10−8 T2.