Institute of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, Berlin 12489, Germany.
Molecules. 2013 Jun 7;18(6):6679-722. doi: 10.3390/molecules18066679.
In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i) ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii) the main characteristics of the generalized isotope effects are worked out, and finally (iii) the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.
为了展示电子顺磁共振(ESR)光谱学与同位素效应之间的关系,我们考虑了三个层次:(i)在一般水平上描述 ESR 光谱学,直至用于解释实验光谱的模型,这些模型超越了通常使用的时间和质量独立自旋哈密顿算子;(ii)阐述了广义同位素效应的主要特征;最后(iii)利用基本的、主要的量子力学效应来描述电子自旋与所选条件下可及的顺磁对象自由度之间的耦合。迄今为止,ESR 参数和相应的模型已经形式化,包括时间和质量相关的影响,并反映了特定的同位素效应。将在 ESR 光谱中的效应之间建立关系,包括自旋弛豫、自旋交换、磁同位素效应、 Jahn-Teller 效应以及零点振动的影响。将展示一些例子,这些例子展示了同位素的影响以及可获取信息的种类。将根据顺磁中心本身以及各自基质中的同位素效应进行区分,直至 ESR 成像技术。结果表明,在 ESR 光谱学中,同位素效应的使用是不可或缺的。