{note:title=Be Careful} I didn't have enough time to type all the equations, so I just scanned them up for now. Still need to add more details to the problems to make them clear. {note} h2. Dynamics \\ {latex} $s(t)=e^{-t/T_{2}}\int P(r)e^{-i\int^{t}_{0}\omega(r,t')dt'}dr$ {latex} \\ ω(r,t') = resonant frequency P(r) = probability distribution * Coherent - when ω is not a function of r (There are no interesting dynamics) * Stationary - when ω is not a function of time (the system can be refocused by a π pulse for any time) * Incoherent - stationary and not coherent, explicitly ω is a function of r (interesting question is the distribution of ω(r) * Decoherent - when ω is a function of time and r, and the t dependence is stochastic/Marchovian (interesting dynamics: distribution of ω(r), spectral density of ω(r) * Periodic - ω is a simple function of time (interesting dynamics: distribution of ω(r) at the characteristic frequency) \\ h3. Periodic !p1.jpg! !p2.jpg! Frequency that an arbitrary location will see \\ {latex} $\omega(t) = \gamma r \frac{\partial B_{z}}{\partial x} cos(\omega _{s} t + \phi)$ {latex} \\ {latex} $exp(i\int^{t}_{0}\omega(t')dt'=exp(i[\gamma \frac{\partial B_{z}/\partial x}{\omega_{s}}r sin(\omega_{s}t+\phi])$ {latex} \\ {latex} $exp^{iRsin\alpha}=\sum J_{k}(R)e^{ik\alpha}$ {latex} for one location in the sample \\ Static Spectrum !p3.jpg! *Problem 1* - Show that for average over φ, we get pure absorptive line-shape, and for a particular isochromat, average over φ in general has dispersive line-shape (Show the response in cylindrical coordinate) - Normal shim: x,y (first order spherical harmonic). If there are terms x^2-y^2, xy, then the sideband will show up at twice Ω - Calculate the FID and the spectrum for rotary vs non-rotary, then plot them on top of each other \\ h3. Nuclear Spin - Zeeman interaction - Chemical shift : ppm variation due to chemistry \-> transform as a tensor (orientation of the molecule matter) \\ {latex}$H_{z}=\omega _{0}I_{z}${latex} \\ {latex}$H_{cs}=-\omega _{0}\sigma I_{z}${latex} \\ !p4.jpg! PAS (Principle axis system) = coordinate system that leave the molecule in diagonal ?? !p5.jpg! ω in transverse plane (slow) can be suppressed if rotation around z-axis is fast !p6.jpg!\\ {latex}$\sigma _{z} \sigma _{z}'${latex} = secular part of the chemical shift, lead to small rotation in x-y direction \\ *Problem 2* - Show that chemical shift tensor \\ {latex} $\sigma = \sigma_{iso} + (\frac{\sigma}{2})(3 cos^{2}\theta -1)- \frac{\delta^{eta}}{4}sin^{2}\theta(e^{i2\phi}+e^{-i2\phi})$ {latex} \\ {latex} $\sigma_{iso}=(\sigma_{xx}+\sigma_{yy}+\sigma_{zz})/3$ {latex} \\ {latex} $\delta=\frac{2}{3}\sigma_{zz}-\frac{1}{3}(\sigma_{xx}+\sigma_{yy})$ {latex} \\ {latex} $\eta=3(\sigma_{yy}-\sigma_{xx})/2(\sigma_{zz}-\sigma_{xx}-\sigma_{yy})$ {latex} \\ - Show that under random rapid motion spins \\ {latex}$< \sigma > = \sigma _{iso}${latex} \\ It average out any non-isometric parts, so we have a homogeneous sample. So the result does not depend on the orientation of the sample. When η = 0 \-> < 3cos(θ)^2 \-1 > = 0, average over sphere - η = 0 ; calculate the line-shape for static powder (constant orientation with magnetic field), η ≠ 0 ; reduce to a summation over η. \[Hint: can be written in elliptical integral, check out appendix I \] - Find σ(θ,φ), powder distribution of the sample (when spinning at the magic angle ?) \\ h3. Decoherence Bloc = field that a test spin would see (every spin averagely see the same distribution of B) !p7.jpg! average vector still pointing along y => \|Bloc> of time or ensemble = 0 !eq1.jpg! !p8.jpg! !p9.jpg! *Problem 3* - What is the contribution of the chemical shift anisotropy to T2? \\ h3. Carl-Purcell Sequence !p10.jpg! !eq2.jpg! *Problem 4* - Look at diffusive attenuation of water rotating in magnetic field gradient. (The faster you rotate it, the effective T2 is approaching T2) \\ h3. Chemical Exchange let !eq3.jpg! !p11.jpg! *Problem 5* - Show the plot of the chemical exchange (when τ\|ΔωA-ΔωB\| approaching 1, the 2 peaks merge at the center) \[Hint: check out appendix F\] \\ h3. Slow Exchange !p12.jpg! choose Δ ≥ τ exchange, Δ << T1, Δ > T2 *Problem 6* - Show that by collect this terms in slow exchange \\ {latex} $e^{i\omega_{A}t_{1}}e^{i\omega_{A}t_{2}} , e^{i\omega_{A}t_{1}}e^{i\omega_{B}t_{2}} , e^{i\omega_{B}t_{1}}e^{i\omega_{A}t_{2}} , e^{i\omega_{B}t_{1}}e^{i\omega_{B}t_{2}}$ {latex} \\ then do phase cycle and collect data set \\ {latex} $cos(\omega_{A/D}T_{1})e^{i\omega_{A/D}t_{2}} , sin(\omega_{A/D}T_{1})e^{i\omega_{A/D}t_{2}}$ {latex} \\ Then we get pure absorptive line-shape |