Development and validation of an integrated computational approach for the modeling of cw-ESR spectra of free radicals in solution:: p-(methylthio)phenyl nitronylnitroxide in toluene as a case study
Development and validation of an integrated computational approach for the modeling of cw-ESR spectra of free radicals in solution:: p-(methylthio)phenyl nitronylnitroxide in toluene as a case study
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溶液中自由基 cw-ESR 光谱建模的综合计算方法的开发与验证：以甲苯中的对甲硫基苯基硝基氧化物为案例研究
DOI：
10.1021/ja065475q
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发表时间：
2006-12-13
影响因子：
15
通讯作者：
Zoleo, Alfonso
中科院分区：
文献类型：
--
作者：
Barone, Vincenzo;Brustolon, Marina;Zoleo, Alfonso
在这项工作中，我们解决的解释，通过从头算集成计算方法，连续波电子自旋共振（cw-ESR）光谱的p-（甲硫基）苯基硝基氮氧化物（MTPNN）溶解在甲苯中。我们的方法是基于确定的自旋哈密顿，平均相对于快速振动运动，磁张量参数（塞曼和超精细张量），其特征在于量子力学密度泛函计算。然后，该系统被描述为一个随机刘维尔方程，包括扩散旋转动力学。扩散转动张量的参数化是由流体力学模型提供的。MTPNN的CW-ESR谱在很宽的温度范围内（155-292 K）进行了模拟，最小程度上依赖于拟合程序，证明灵敏的ESR谱和复杂的建模相结合可以非常有助于提供分子系统的结构和动力学信息。
In this work we address the interpretation, via an ab initio integrated computational approach, of continuous wave electron spin resonance (cw-ESR) spectra of p-(methylthio) phenyl nitronylnitroxide (MTPNN) dissolved in toluene. Our approach is based on the determination of the spin Hamiltonian, averaged with respect to fast vibrational motions, with magnetic tensor parameters (Zeeman and hyperfine tensors) characterized by quantum mechanical density functional calculations. The system is then described by a stochastic Liouville equation, with inclusion of diffusive rotational dynamics. Parametrization of diffusion rotational tensor is provided by a hydrodynamic model. Cw-ESR spectra of MTPNN are simulated for a wide range of temperatures (155-292 K) with minimal resorting to fitting procedures, proving that the combination of sensitive ESR spectroscopy and sophisticated modeling can be highly helpful in providing structural and dynamic information on molecular systems.