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  • >> Sticks.

  • All right, but we're going to talk about spins today.

  • Not about sticks.

  • So I want to continue our discussion of the concepts

  • and theory behind NMR spectroscopy and again,

  • this is not going to be about math or anything to that extent.

  • But we're going to be thinking very, very qualitatively.

  • All right, so when we last left things we had said

  • that there are two spin states

  • for a dipolar nucleus like a proton or C13.

  • There's spin up and spin down,

  • and if you have an applied magnetic field there's a small

  • energy difference between the spin up state,

  • what we're calling the Alpha state and the spin down state,

  • what we're calling the Beta state.

  • And because that energy difference is

  • so small unlike IR spectroscopy or electronic spectroscopy,

  • UV Vis spectroscopy where the energy differences are very big

  • and all of your molecules are in the ground state,

  • here there's only a miniscule number of nuclei

  • in the lower state more than the number in the upper state.

  • We said if there are -- if we take 2 million protons,

  • out of those 2 million protons depending

  • on the applied magnetic field, it will be 50 or 80

  • or thereabouts difference in population.

  • In turns out that difference in population is going

  • to be extremely important because it is only

  • that differential population that's going

  • to be able to get us a signal.

  • All right, so if we think about things

  • in an XYZ coordinate frame, and I'll talk more

  • about NMR spectrometer in a second and how it works.

  • But imagine for a moment we have some coordinates,

  • so the X coordinate is coming out of the plane,

  • the Y coordinate is in the plane and the Z coordinate is pointing

  • up and we're going to have our applied magnetic field BNOT

  • pointing upwards.

  • That kind of makes sense.

  • These super conducting magnets are always vertical

  • because you've got this big pot of liquid helium surrounded

  • by a vacuum vessel, surrounded by liquid nitrogen,

  • surrounding by a vacuum vessel.

  • And, those small amounts of population,

  • that small differential of population with spin up is going

  • to give rise to a net magnetization.

  • Now, in other words a way to think about this is for most

  • of our cases we're going to have one nucleus pointing up,

  • one nucleus pointing down in their spin

  • and there's no net vector here.

  • Those vectors cancel each other out.

  • But for that small differential of access vectors you're going

  • to have some net magnetization along the Z-axis.

  • Now, the ay it works, when you apply a magnetic field is you

  • actually have those vectors that are processing around.

  • So in other words they are processing

  • at that resonant frequency, at the Lamar Frequency

  • at 500 megahertz for 117,500 Gauss magnet.

  • So we actually can represent this by saying okay,

  • we've got spin sort of pointing in every which way,

  • and I'll just draw two directions.

  • They're all processing around.

  • So remember, remember this is only the differential population

  • that we're worried about because already for every one

  • where you have one up and you have an opposing one spin

  • down those vectors are going to cancel each other out.

  • Now the other thing is they're not quite on axis.

  • In other words they're not like this.

  • It's like a gyroscope if you've ever hung it from a string,

  • the gyroscope doesn't --

  • who's hung a gyroscope from a string as a kid?

  • The gyro in physics lab or something.

  • The gyroscope doesn't hang vertically,

  • it kind of hangs off axis and goes around like this.

  • But if you think about it, since those spins are not bunched

  • up for every one that's processing

  • like this there's another one that's opposite it.

  • So in other words if were just like this you'd say,

  • oh there's a net magnetization along the Z axis

  • but also a net magnetization along the Y axis.

  • But there are other spins that are like this

  • and they're all going around.

  • So everything is canceling

  • out except the net magnetization along the Z axis.

  • All right, what I want you to imagine right now is

  • that we're going to place a coil along the X axis and we're going

  • to put energy into that coil.

  • We're going to apply a magnetic force.

  • And I want you to think classically

  • because the quantum mechanical thing is going

  • to be we'll flip the spins.

  • I'll show you that in a second.

  • But you have your net magnetization along the Z axis,

  • and think back to classical physics.

  • If I apply a force along the X axis, right hand rule and all

  • of that good stuff, we rotate our vector downward.

  • So after we apply a pulse, I'll just say a pulse.

  • If here's out net magnetization,

  • when we apply an RF pulse our net magnetization moves along

  • the Y axis, and so I guess if I want

  • to actually represent it I'll just say XYZ,

  • and I'll say here's our net magnetization.

  • And as you'll see in a moment we're going

  • to have continued procession.

  • And again, if you're worried about the fact that all

  • of our vectors are not lining up, that they're all processing

  • like this, just think as I apply a pulse

  • and drive my magnetization from the Z axis onto the Y axis,

  • the vector sum is right along the Y axis even though there are

  • some that are like this, I drive it down.

  • They're countering each other.

  • There are some like this, I drive it down.

  • They're countering each other.

  • And so our net magnetization ends up a long the Y axis.

  • Does that make sense?

  • All right, lets come back to our spins to see what this means.

  • So, the way I was trying last time

  • to represent this very small difference

  • between the Alpha state and the Beta state was

  • to show some vectors, some spins pointing up in the Alpha state.

  • And some spins pointing down in the Beta state,

  • and to try to represent this miniscule difference

  • in population what I did for the purpose

  • of my drawing was I drew 6 with spin up in the alpha state and 4

  • with spin down in the Beta state.

  • >> [Inaudible] nuclei right?

  • >> Those are representing exactly the spins

  • of individual nuclei.

  • So in other words, if we had a mole of --

  • or more realistically if we had a millimole of CHCL3,

  • proiochloroform [assumed spelling] in our NMR tube,

  • what this would represent would be the different,

  • the nuclei of the hydrogen there and we would have out of

  • that millimole of nuclei we would have a small access

  • in the Alpha state and they would all be processing.

  • All right, so if we apply an RF pulse, and now I'm going

  • to be a little bit specific, if we apply a pulse long enough

  • that it's what's called a 90 degree RF pulse or a pi over 2.

  • That's just radians and degrees, your choice

  • and they get used interchangeably.

  • What that does is it equalizes the population of Alpha

  • and Beta state, so I'll represent

  • that by 5 spin up and 5 spin down.

  • And this situation is exactly the situation that we have

  • at the end of my little drawing

  • over on the left-hand blackboard.

  • In other words here's our net magnetization.

  • And so the key is now we have no net magnetization spin up,

  • no net magnetization spin down,

  • but the very important point is we have the net magnetization

  • focused along the Y axis.

  • It is not diffuse, it is not pointing in all directions.

  • We actually have net magnetization in the XY plane.

  • And if we apply a longer pulse, a more powerful RF pulse,

  • so again I will represent our 6 little arrows

  • and 4 little arrows representing our differential populations

  • of the Beta state.

  • If we apply a more powerful RF pulse,

  • what we call a pi RF pulse

  • or a 180 degree RF pulse I can invert the population.

  • In other words I will represent that by 4 arrows pointing up

  • and 6 arrows pointing down.

  • And if I want to draw that on my diagram,

  • can anyone tell me what I do with my net magnetization

  • on my little XYZ diagram at this point?

  • >> Down.

  • >> It's going to point down, exactly.

  • All right, and this is the damming thing.

  • Well, one of the many damming things

  • about NMR spectroscopy is no matter what you do

  • with your pulses you are limited to the difference in population

  • that occurs between the Alpha and Beta state,

  • and later when we start to talk