Dynamics of NaHSeO3 and NaHSeO4 single crystals by observation of 1H and 23Na spin-lattice relaxation.
The 1H and 23Na spin-lattice relaxation times of NaHSeO3 and NaHSeO4 single crystals grown by the slow evaporation method were measured. The phase transitions of the two crystals were studied using differential scanning calorimetry (DSC), and the environments of the 1H and 23Na nuclei in these crystals were investigated by means of 1H and 23Na NMR spectroscopy. The DSC results show that NaHSeO3 crystals do not undergo phase transitions, whereas for NaHSeO4 crystals there is a small endothermic peak at 419 K. The dimers in NaHSeO3 stabilize its structure to the extent that there are no phase transitions even in the presence of disordered hydrogen bonds. In addition, the NMR results indicate that the temperature dependencies of T1 for the 1H and 23Na nuclei in the two hydrogen-bonded crystals-the NaHSeO3 crystal with 3-coordinated SeO3 and the NaHSeO4 crystal with 4-coordinated SeO4--are significantly different. The different trends in T1 for Na in the two crystals are accompanied by different shifts of the oxygen atoms from the 3-coordinated SeO3 and the 4-coordinated SeO4 species around the Na+ ions. Thus, although the two crystals have hydrogen-bonded structures, the differences between the hydrogen bonding of the 3-coordinated SeO3 in NaHSeO3 and the hydrogen bonding of the 4-coordinated SeO4 in NaHSeO4 result in different T1 temperature dependences and different phase transitions.
Lim
Ae Ran
AR
Department of Science Education, Jeonju University, Jeonju 560-759, Republic of Korea. aeranlim@hanmail.net
Jang
Seo Won
SW
Chang
Jin-Hae
JH