Pavone Michele, Cimino Paola, De Angelis Filippo, Barone Vincenzo
Dipartimento di Chimica, Università di Napoli FedericoII, Complesso Universitario di Monte Sant'Angelo Via Cintia, Italy.
J Am Chem Soc. 2006 Apr 5;128(13):4338-47. doi: 10.1021/ja0574872.
The nitrogen isotropic hyperfine coupling constant (hcc) and the g tensor of a prototypical spin probe (di-tert-butyl nitroxide, DTBN) in aqueous solution have been investigated by means of an integrated computational approach including Car-Parrinello molecular dynamics and quantum mechanical calculations involving a discrete-continuum embedding. The quantitative agreement between computed and experimental parameters fully validates our integrated approach. Decoupling of the structural, dynamical, and environmental contributions acting onto the spectral observables allows an unbiased judgment of the role played by different effects in determining the overall experimental observables and highlights the importance of finite-temperature vibrational averaging. Together with their intrinsic interest, our results pave the route toward more reliable interpretations of EPR parameters of complex systems of biological and technological relevance.
通过一种综合计算方法，包括卡-帕里尼罗分子动力学和涉及离散-连续介质嵌入的量子力学计算，研究了原型自旋探针（二叔丁基氮氧化物，DTBN）在水溶液中的氮各向同性超精细耦合常数（hcc）和g张量。计算参数与实验参数之间的定量一致性充分验证了我们的综合方法。对作用于光谱可观测量的结构、动力学和环境贡献进行解耦，能够对不同效应在确定整体实验可观测量中所起的作用进行无偏判断，并突出了有限温度振动平均的重要性。除了其内在的研究价值外，我们的结果还为更可靠地解释具有生物学和技术相关性的复杂系统的电子顺磁共振参数铺平了道路。
