波谱学杂志 ›› 1986, Vol. 3 ›› Issue (3): 229-234.

• 研究论文 • 上一篇    下一篇

未掺杂反式聚乙炔(CH)x中核自旋晶格弛豫-孤子-维扩散模型

吴肖令   

  1. 华东师范大学
  • 收稿日期:1985-10-16 修回日期:1986-03-23 出版日期:1986-09-05 发布日期:2018-01-23

NUCLEAR SPIN-LATTICE RELAXATON IN UNDOPED TRANS-POLYACETYLENE(CH)x A 1D-SOLITON DIFFUSION MODEL

Wu Xiaoling   

  1. Dept. of physics, East-China Normal Univ.
  • Received:1985-10-16 Revised:1986-03-23 Online:1986-09-05 Published:2018-01-23

摘要: Nechtschein等人报道并分析了反式聚乙炔中质子自旋晶格弛豫时间对拉摩频率ω和温度T的依赖关系。观察到了质子自旋晶格弛豫速率T1-1ω-1/2的正比关系。但是在高频段,T1-1ω-1/2关系发生偏离,且温度越低,发生偏离的频率也越低。
本文用另一种方法对这些实验结果作了分析。首先,论证了孤子一维扩散模型的合理性。排除了质子弛豫速率∝ω-1/2的另一种解释,即仅仅是核自旋向着静止的顺磁中心扩散。孤子能处在运动状态或静止状态。当温度降低时,发生两个效应,即越来越少的孤子处于运动状态,且运动孤子的扩散系数减小。只有扩散的孤子对所观察到的质子弛豫有贡献,而固定孤子的贡献可以忽略。其次,描述了运动孤子的一维随机行走模型,计算了它的相关函数和谱密度函数。质子自旋晶格弛豫速率是:
其中C是运动孤子的浓度,τ是运动孤子沿链跳跃时,渡越相邻位置的跳跃时间,ω是质子的拉摩频率。
这个公式揭示了质子弛豫速率的频率和温度依赖关系的主要特征。它和Nechtschein的测量结果拟合得很好。从拟合中可以得到各个温度下运动孤子的跳跃时间和相对浓度。

Abstract: The proton spin-lattice relaxation times in transpolyacetylene versus Larmor frequency ω and temperature T were reported and analyzed by Nechtschein et. al. (2). The ω-1/2 dependence of the proton spin-lattice relaxation rate T1-1 in trans-polyacetylene was obaerved. However, at high frequency the data deviate from ω-1/2 at a certain frequency which becomes lower and lower as temperature is decreased.
These experimental results are analyzed in a different way in this paper. First, the justification for 1D-soliton diffusion model is discussed. The interpretation whereby only nuclear spin flip diffusion to static paramagnetic centers gives rise to ω-1/2 behaviour in the proton relaxation rate is ruled out. Solitons can be either in mobile state or in fixed state. As the temperature decreases two effects take place, that is, there are fewer and fewer solitons in the mobile stale and the diffusion coefficient of mobile Solitons decreases. Only diffusive solitons are responsible to the observed proton relaxation, while the contribution from fixed solitos are negligible. Secondly, a 1D random walk model for mobile solitons is described and its correlation function and spectrum density function are calculated. The proton spinlatticc relaxation rate is

where C is the density of mobile soliton, τ is the hopping time of mobile soliton between adjacent sites along the chain, and ω is the Larmor frequency of proton.
Theoretical curves obtained from this formula fit with Nechtscheins measurement very well. The hopping time and relative density of mobile solitons at various temperatures are extracted,