Ab initio calculations of electric field effects on the g-tensor of a nitroxide radical
Ab initio calculations of electric field effects on the g-tensor of a nitroxide radical
复制标题
从头计算电场对硝基氧自由基 g 张量的影响
DOI：
10.1063/1.1416177
复制
发表时间：
2001
影响因子：
4.4
通讯作者：
D. Budil
中科院分区：
文献类型：
--
作者：
Zhebo Ding;A. F. Gullá;D. Budil
利用瑞利-薛定谔微扰理论的中间能级，基于不受限制的hartrei - fock从头计算，计算了外加电场对氮氧化物自旋标签磁参数的影响。该理论对选定的简单模型有机自由基进行了测试，并给出了与先前计算和实验值比较良好的电子g张量。然后用有限场方法计算了局部静电场对较大的硝基2,2,5,5-四甲基-3,4-脱氢吡啶-1-氧（TMDP）的影响。该方法略微低估了TMDP的gx和gy，但预测的这些量随场的变化与最近使用高频（220 GHz）电子顺磁共振的实验观测结果非常吻合。结果用Mims先前给出的表征金属中心线性电场效应的现象学形式表示。
The effects of applied electric fields on the magnetic parameters of a nitroxide spin label have been calculated using an intermediate level of Rayleigh–Schrodinger perturbation theory based on unrestricted Hartree–Fock ab initio calculations. The theory is tested for selected simple model organic radicals and gives electronic g-tensors that compare well with previous calculations and experimental values. The method is then applied to calculate effects of a local electrostatic field on the larger nitroxide radical, 2,2,5,5-tetramethyl-3,4-dehydro pyrrolidine-1-oxyl (TMDP) using a finite field approach. The method slightly underestimates the gx and gy of TMDP, but the predicted shifts in these quantities with field are in excellent agreement with recent experimental observations using high-frequency (220 GHz) electron paramagnetic resonance. Results are expressed in terms of the phenomenological formalism given earlier by Mims to characterize linear electric field effects in metal centers.
影响因子：
6.8
作者：
Hubbell, WL;Gross, A;Lietzow, MA
通讯作者：
Lietzow, MA