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A Description of the Nuclear Magnetic Resonance Spectrometer Michael Hunecke Atoms, Molecules, Reactions Fall 2013

Modern application of Nuclear Magnetic Resonance is prominent in the Medical field in the form of Magnetic Resonance Imaging (MRI), which allows for the creation of extremely detailed pictures of any possible cross- sectional plane in the human body. In Chemistry, NMR is used to examine structures of significant compounds, and the NMR spectra are useful for gaining information on the dynamic behavior of compounds within their experimental environment. This document will focus on the physics of the apparatus itself, with incidental statements regarding the history of NMRs development where pertinent. Electronic spin, the third quantum number, is a concept that allows a determination of the energy levels that exist between atoms, as d- orbitals are split and bonds are formed and broken. Atomic spin takes into consideration the movement of the entire nucleus and its components by examining what can be described as a net dipole moment for an entire sample, and this is the central principle upon which Nuclear Resonance Spectroscopy is founded. Importantly, it is the atoms with odd numbers of protons and neutrons that display a non-zero spin, and is exclusively particles with this characteristic (1H, 13C for instance) that NMRs unique sensitivities are able to capture data from.

At the heart of the instrument that is a Nuclear Magnetic Resonance Spectrometer lies a powerful electromagnet that is fitted with multiple coils that are

able to conduct current individually. The purpose of this is to set up a primary magnetic field that a sample can be oriented in and a secondary, orthogonal field designed to perturb the nuclei in the sample from their spins in the steady field. The NMR system contains several interfaced modules to perform and record the results, and the roles of each component can be better understood if the theory behind Nuclear Magnetic Resonance is briefly described. As pointed out above, only particles with odd numbers of protons and neutrons will exhibit non- zero spin, specifically, if the total number of protons and neutrons is odd, the nucleus is considered to have a half- integer spin, (1/2, 3/2, 5/2 . . .), and if both the number of protons and the number of neutrons are odd, then the nucleus is considered to have an integer spin (1, 2, 3, . . ), and just like electrons, they have low and high energy states, depending on whether their dipole moment spins with or against the polar direction of the magnetic field they are in. Between these two energy states is a quantity referred to as the Lamor Frequency and is given by:

= B0
which means the angular frequency of the spin is the magnetic field (B) offset by the magnetogyric ratio (), itself figure relating angular momentum to Planks constant h. Hydrogen nuclei have the highest magnetogyric ratio, and the relationship between frequency and change of energy is stated in Skoog: . . . transitions between energy states can be brought about by absorption or emission of electromagnetic radiation (500). There is energy associated with frequency in that

E= h and in this case the difference between high and low energies is equaled to the angular frequency of the precession around the z- axis. Here it is essential to imagine the idea of precession as it is exhibited by nuclei in a magnetic field. It may be appropriate to visualize the classical physics demonstration of angular momentum where a bicycle wheel is suspended by a line connected to one side of its axle, and spun. Through its own momentum it is able to hold itself nearly parallel to the line, and no matter what angle it is tilted at, the wheel itself rotates about the axis at a uniform time, eventually settling perpendicular to the line again. The conical shape it traces at an angle around the z axis of the line describes precession, and the angular velocity is the Lamor Frequency in our atomic case. In a group of nuclei, there will be a combination of low and high energy spins, with a majority tending to the low energy state. Thermal collisions have the capacity to knock nuclei into a higher energy state, and the Boltzman Distribution illustrates the ratio of the amount of high and low energy nuclei:

Nhi/Nlo= e-Bo/kT
where k is Boltzmans constant. Creating a homogenous B field that is strong enough to overcome the condition of thermal collisions is necessary because what is important is the difference between the high and low states, and more high energy states brings the ratio closer to even.

Once a sample of nuclei are spinning in their position around the axis of the B field, (it is useful to visualize this in 3 dimensional Cartesian coordinates as two cones with their tips meeting at the point of origin, themselves centered on a shared vector leaning slightly off the z- axis) it is possible to affect these nuclei from the transverse (x,y) plane. The precession of nuclei, rotating at the Lamor frequency, if passed through a solenoid coil theoretically wrapped around the x-axis, would by Faraday induction generate current through the wire of an identical frequency. Incidentally, it is this same procedure carried out by Bloch, Hansen, and Pacard that is notated as the birth of NMR, in 1946, and succeeded in identifying the resonant frequency of a group of nuclei in a magnetic field. From here the principle is expanded to not only deduce the energy of absorption of an atom via equating its magnetic displacement to a measured frequency, but to also radiate orthogonally electromagnetic waves onto the sample to temporarily excite the nuclei along the transverse plane. In measuring the return to the initial polarized state of the nuclei, the relaxation, the methods of determining molecular and electronic structure are established. The first commercially produced apparatus utilized continuous wave (CW) NMR, wherein the frequency of the radiated RF signal is adjusted through the resonance band and recorded, and this method remained the standard for many years because it permits sequential observation of each of the many resonance lines in a spectrum (Becker 297). However pulse, or Fourier Transform (FT) NMR has since become predominant, largely due to its ability to capture discrete pulses of

orthogonal RF followed by relaxation, frequently recorded and irradiated with the same coil. This is the case with the unit on campus at TESC, a Mercury/Oxford 400/54 (whose mother company, Albion, produced the first NMR model), that records a pulse/relaxation, amplifies the signal, digitizes it, and sends it to a host computer that displays the frequency spectrum of the sample. This wave is referred to as free induction decay (FID). Because of the combination of technologies at work in an NMR system, there is indeed a science to the instrument itself. The homogenous magnetic field has, over the years, been made more consistent and stronger through improved magnet design, and the ability to create a superconducting environment for the solenoid by submerging the entire unit in a Dewar containing liquid nitrogen and liquid helium further increased both strength and sensitivity in NMR operation. Modern software enables accurate monitoring of the waveform, and also can be used to perform the very delicate task of calibrating the magnetic field such that it traverses the x- axis at a perfectly right angle, a process referred to as shimming. In fact, the multiple coils mentioned at the top of this piece are used for this purpose, and in researching the details of this complex instrument a significant amount of time has been spent observing a technician performing this operation: Once the unit is assembled, a sample sample, is placed in the center of the magnet and the current through 14 individual coils is slightly adjusted while monitoring the resonance spike on a computer screen in an effort to both center the spike and make the shape of the line width uniform on both sides of the reading. The process resembles an experiment

and the results indicate there is much to gather from the very function of the Nuclear Magnetic Resonance Spectrometer.