自旋动力学-第三章.ppt

* NMR 谱特征：位置，形状，宽窄 影响因素 提供分子结构、运动信息 NMR 谱（频域）：I(?) 第三章：核磁共振谱 Chapter 3 NMR Spectroscopy I ? 强度随频率分布 3.1 简单脉冲序列 （ Simple Pulse Sequence） sfid (t)= Meq exp(iω0t) exp{?t/T2} fourier transformation t T2, 1/T2: transverse relaxation time, rate Experimental T2: Fid or line width FID (时域） NMR谱 (频域） 匀场？ frequency, 1 1/2 Full width at half-height. absorption Lorentzian angular frequency, Full width at half-height = 1/(?T2)~1/T2 relaxation rate 3.2 Simple spectrum FID Decay: 指数衰减：xp{?t/T2} Lorentzian 吸收线型 线宽 Gauss衰减FID： exp{? (t/T2)2} ?? NMR谱： exp{?[(?-?0)T2/2]2} 3.34/T2 ? Gauss线型 3.3 Spectral Frequencies 3.3 谱频率 (lab frame静止) : ?ref ?0 ?0 Cos(?reft) Relative Spectral Frequencies: ?0 = ω0 ? ωref ?= ω ? ωref the resonance offset or the Larmor frequency in the rotating frame Relative Spectral Frequencies: Case of Positive Gyromagnetic Ratio 3.4相对谱频率 (rotating frame旋转) : 3.5 Inhomogeneous Broadening Difficult : a perfectly homogeneous magnetic field ?The sample itself tends to distort the applied magnetic field, because of its magnetic susceptibility. *In some NMR experiments, spatially dependent magnetic fields are deliberately applied, using specially designed additional field coils. This is the case in, for example, NMR imaging experiments. 非均匀宽化 500*106 Hz/11.7T = 4274 Hz/G = 0.4 Hz/0.0001 G 500 MHz (11.7T)谱仪 0.4 Hz ?B~0.0001 G 磁场均匀度 例1：不均匀磁场（外磁场，样品（外部形状，内部空洞等）） pure waterχ = ?9.05 × 10?6. Binduced=-??0M=-??B0~ 1 G ?形状各向异性因子 ?=4?, 4?/3, …. 0 Binduced=-??0M M 非均匀退磁场 Binduced B0 一维投影 Z 不均匀外磁场 重要应用MRI Inhomogeneous Broadening 样品不同位置，取向，化学环境等 rf 照射 Burning a hole 烧个洞 非均匀宽化 化学位移各向异性 3.7 Chemical Shifts (CH3CH2OH) ?核周围电子环境（电子自旋或电荷）the nuclear Larmor frequency depends on the local electronic environment. 1. 化学位移 (chemical shift)：抗磁材料 diamagnetic materials, 2. 奈特位移 （Knight shift）：金属和超导材料 metals and superconductors, 3. 顺磁位移 （paramagnetic shift）：顺磁材料 paramagnetic substances. ?核周围核自旋环境The Larmor f