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14N 核四极共振研究氢键有机反铁电体 55DMBP-H2ca 和 1,5-NPD-H2ca 中的相变和分子动力学。

A 14N nuclear quadrupole resonance study of phase transitions and molecular dynamics in hydrogen bonded organic antiferroelectrics 55DMBP-H2ca and 1,5-NPD-H2ca.

机构信息

Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.

出版信息

Phys Chem Chem Phys. 2011 May 28;13(20):9165-72. doi: 10.1039/c0cp02873h. Epub 2011 Apr 11.

Abstract

The temperature dependence of the (14)N NQR frequencies has been measured in antiferroelectric and paraelectric 55DMBP-H(2)ca and 1,5-NPD-H(2)ca. In both compounds we observe two non-equivalent nitrogen positions (N(+)-H···O(-) and N···H-O) in the antiferroelectric phase. The two nitrogen positions become equivalent (N···H···O) in the paraelectric phase. The critical exponent of the local antiferroelectric order parameter has been determined from the NQR data. The principal values of the quadrupole coupling tensor correlate in both compounds. The correlation diagrams clearly show how a proton migrates from the antiferroelectric position towards the paraelectric position in the bifurcated hydrogen bond on increasing the temperature. A slow motion has been observed in 55DMBP-H(2)ca by the (1)H and (14)N spin-lattice relaxation. An analysis of the spin-lattice relaxation data suggests a slow exchange between two non-planar conformations of the bipyridine molecule.

摘要

已在反铁电相和顺电相的 55DMBP-H(2)ca 和 1,5-NPD-H(2)ca 中测量了 (14)N NQR 频率对温度的依赖性。在这两种化合物中,我们观察到反铁电相中存在两个不等效的氮原子位置(N(+)-H···O(-) 和 N···H-O)。在顺电相中,两个氮原子位置变得等效(N···H···O)。从 NQR 数据确定了局部反铁电有序参数的临界指数。在这两种化合物中,四极耦合张量的主值相关。相关图清楚地显示了随着温度的升高,质子如何从反铁电位置向分叉氢键的顺电位置迁移。在 55DMBP-H(2)ca 中,通过 (1)H 和 (14)N 自旋晶格弛豫观察到缓慢运动。自旋晶格弛豫数据的分析表明,联吡啶分子的两个非平面构象之间存在缓慢交换。

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