129Xe NMR chemical shift in Xe@C60 calculated at experimental conditions: Essential role of the relativity, dynamics, and explicit solvent
129Xe NMR chemical shift in Xe@C60 calculated at experimental conditions: Essential role of the relativity, dynamics, and explicit solvent
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在实验条件下计算的 Xe@C60 中的 129Xe NMR 化学位移：相对论、动力学和显式溶剂的重要作用
DOI：
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发表时间：
2013
影响因子：
3
通讯作者：
M. Straka
中科院分区：
文献类型：
--
作者：
S. Standara;P. Kulhánek;R. Marek;M. Straka
用分段近似方法计算了Xe@C60在液体苯中的各向同性核磁共振化学位移(CS)，以真实地模拟实验条件，评价不同物理因素对129Xe核磁共振化学位移的影响。通过对嵌入苯分子的周期盒中Xe@C60体系的分子动力学轨迹计算的129Xe核磁屏蔽平均值，得到了129Xe的屏蔽常数。相对论修正是在Breit-Pauli微扰理论(BPPT)水平上添加的，包括溶剂，并被动态平均。结果表明，Xe@C60体系的内部动力学贡献约占总的非相对论核磁共振CS的8%，而动力溶剂的影响又增加了8%。动态平均相对论效应对总计算的~(129)Xe核磁共振CS的贡献率为9%。最终的理论值172.7 ppm与实验的~(129)Xe CS值179.2 ppm符合得很好，在模型的估计误差范围内。所提出的计算协议可作为计算不同Xe原子客体系统中~(129)Xe核磁共振参数的原型。©2013 Wiley期刊，Inc.
The isotropic 129Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the 129Xe NMR CS. The 129Xe shielding constant was obtained by averaging the 129Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit–Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated 129Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental 129Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of 129Xe NMR parameters in different Xe atom guest–host systems. © 2013 Wiley Periodicals, Inc.
影响因子：
15
作者：
Chambers, Jennifer M.;Hill, P. Aru;Aaron, Julie A.;Han, Zhaohui;Christianson, David W.;Kuzma, Nicholas N.;Dmochowski, Ivan J.
通讯作者：
Dmochowski, Ivan J.
影响因子：
7.8
作者：
Taratula, Olena;Dmochowski, Ivan J.
通讯作者：
Dmochowski, Ivan J.
影响因子：
8.4
作者：
Seward GK;Bai Y;Khan NS;Dmochowski IJ
通讯作者：
Dmochowski IJ