Nuclear Magnetic Resonance N.

Chandrakumar
r The magnetic moment associated with a spin is given by:

Zeeman Hamiltonian

Here, is the magnetogyric ratio and I , the (dimensionless) spin angular momentum operator. The energy of interaction of a spin with a static (dc) magnetic field (Zeeman field) is then given by the following relation:

r r = hI

r r r r H = B = h I B

It is the convention to adopt the direction of the magnetic field as the z-axis, B0 being its intensity. With this choice of co-ordinate system, we have:

E = hB0 mI
The result is a set of (2I+1) energy levels that are equally spaced, the spacing being hB0. Dynamically, the spin magnetic moments precess about the magnetic field, the magnitude of the torque being the derivative wrt orientation angle of the energy of the magnetic moment in the magnetic field, equal in turn to the rate of change of angular momentum:

H = hB0 I z

r dI r r C h = B dt r d r r = B dt

This vector equation may be solved as a set of coupled differential equations r in the components of the magnetic moment. Because B represents a static (dc) magnetic field, one finds that the z-component of magnetic moment is independent of time, while the x- and y-components oscillate in time with the angular frequency 0 = B0, which is the so-called Larmor precession frequency and also represents the energy level difference in units of angular frequency.

NMR Spectroscopy NMR Spectroscopy involves the interaction of nuclear magnetic moments with the magnetic component of resonant electromagnetic radiation, the experiment being carried out with the sample placed in a Zeeman magnetic field, in which nuclear spins (magnetic moments) precess at a characteristic Larmor frequency. NMR transitions are magnetic dipole transitions, and obey a selection rule for the change allowed in the magnetic quantum number m (component of spin angular momentum in the direction of the Zeeman field): m = 1 The frequency of an NMR transition is governed by:

0 = ( ) B0
The transition frequency is governed by the intensity of the Zeeman field, as well as the magnetogyric ratio of the spins, a characteristic of the nuclear isotope in question. It turns out however that the magnetic field sensed at the nucleus is modified by the local environment, primarily the electron density around the nucleus in question and in its neighborhood:

E = hB0

0 = ( ) B0 (1 )

i i = B0 (1 i ) + J ij m j 2 j

Here, is a screening (or shielding constant), that describes the effect of the surrounding electron density including neighbouring groups and also electron circulation in aromatic rings in modifying the field intensity at the site of the nucleus. In addition, the NMR resonance frequency is modified by internuclear, through-bond scalar spin-spin coupling J, which relates to the functional groups in the neighborhood of the probe nuclear spin. Taking both these effects into account, the resonance frequency of the ith nuclear spin may therefore be given by:

Bloch Equations The magnetization of an ensemble of non-interacting spins with spin quantum number I (eg. atomic nuclei in a molecule, or unpaired electrons in molecules or free radicals), when they are immersed in a magnetic induction (or magnetic field of intensity) B0 along the z direction is given by the Curie susceptibility:

M 0 = 0 B0

Here the Curie susceptibility 0 is given by: N 2 h 2 I ( I +1)

0 =

3 kT

N is the number of spins per unit volume; is the magnetogyric ratio (a property of the spin) and T the absolute temperature. This corresponds to a state of thermal equilibrium governed by the Boltzmann distribution of spin populations among the (2I+1) allowed energy levels of the spin system, the ratio of populations of two energy levels being given by:

Ni ( E E ) = exp ikT j Nj

In thermal equilibrium, the magnetization of the ensemble is parallel to the direction of the magnetic field, while components of magnetization transverse (perpendicular) to B0 vanish. Dynamically, the spins precess around B0 with the Larmor frequency:

0 = B0

This corresponds to the fact that the energy difference between successive energy levels of the (2I+1) level system is h0. The Bloch equations are phenomenological equations that describe the return of the spin magnetization components to their equilibrium values following the creation of a non-equilibrium condition by suitable means.

dM z dt dM x dt dM y dt

( M z M0 )
T1

x =M T2

My T2

Clearly, the Bloch equations imply that the return to equilibrium is governed in general by two first order rate constants, T21 pertaining to the transverse components and T11 to the longitudinal component of magnetization. The former is known as the transverse or spin-spin relaxation rate, while the latter is the longitudinal or spin-lattice relaxation rate. Relaxation corresponds to radiationless transitions of the spin system, that occur, for example, in readjusting energy level populations to their equilibrium values. Energy conservation requires that the energy released when a radiationless transition occurs from a higher to a lower energy level be soaked up by the other degrees of freedom of the system in which the spins are embedded (eg. molecules in liquid, solid or gaseous phase). This would require that there exist such a motional mode of the system that can accept the quantum of energy released. Accordingly, the efficiency of longitudinal relaxation is governed by the spectral density (ie, energy available in motions) at the Larmor frequency and at double the Larmor frequency. Measurement of T1 can therefore throw considerable light on molecular motions. It may be noted that transverse relaxation is governed in addition by the spectral density at zero frequency. The exponential time decay of nonzero transverse magnetization implied by the Bloch equations leads to the Lorentzian lineshape of magnetic resonance signals in solution state, where the approximation of non-interacting spins is often reasonable. In this situation, the relation between the full linewidth at half maximum height (1/2) and the relaxation rate, T21, is given by:

1 =
2

1 T2

In the solid state on the other hand, lineshapes are often Gaussian. Lineshapes that are intermediate to these two extremes are also often encountered in magnetic resonance spectra, and are termed the Voigt lineshape.