Sachleben Joseph R, Gaba Janet, Emsley Lyndon
Otterbein College, Chemistry Department, Westerville, OH 43081, USA.
Solid State Nucl Magn Reson. 2006 Feb;29(1-3):30-51. doi: 10.1016/j.ssnmr.2005.09.009. Epub 2005 Nov 9.
We investigate the effect of magic angle spinning on heteronuclear spin decoupling in solids. We use an analytical Floquet-van Vleck formalism to derive expressions for the powder-averaged signal as a function of time. These expressions show that the spectrum consists of a centerband at the isotropic frequency of the observed spin, omega(0), and rotational decoupling sidebands at omega(0)+/-omega(1)+/-momega(r), where omega(1) is the decoupling field strength and omega(r) is the rotation frequency. Rotary resonance occurs when the rotational decoupling sidebands overlap with the centerband. Away from the rotary resonance conditions, the intensity of the centerband as a function of omega(r)/omega(1) is simply related to the total intensity of the rotational decoupling sidebands. Notably, in the absence of offset terms it is shown that as omega(1) decreases, the centerband intensity can decrease without any associated broadening. Furthermore, the centerband width is shown to be independent of spinning speed, to second order for the effects we consider. The effects of I spin chemical shift anisotropy and homonuclear dipolar couplings are also investigated. The analytical results are compared to simulations and experiments.
我们研究了魔角旋转对固体中异核自旋去耦的影响。我们使用解析弗洛凯 - 范弗莱克形式理论来推导粉末平均信号随时间变化的表达式。这些表达式表明,谱由位于观测自旋的各向同性频率ω(0)处的中心带以及位于ω(0)±ω(1)±mω(r)处的旋转去耦边带组成,其中ω(1)是去耦场强,ω(r)是旋转频率。当旋转去耦边带与中心带重叠时会发生旋转共振。在远离旋转共振条件下,中心带强度作为ω(r)/ω(1)的函数与旋转去耦边带的总强度有简单的关系。值得注意的是,在没有偏移项的情况下,结果表明随着ω(1)减小,中心带强度可以降低而没有任何相关的展宽。此外,对于我们所考虑的效应,中心带宽度被证明与旋转速度无关,至二阶近似。我们还研究了I自旋化学位移各向异性和同核偶极耦合的影响。将解析结果与模拟和实验进行了比较。