Nuclear Magnetic Resonance

Quantum Numbers

Principal quantum number (n) : the potential energy of electron Azimuthal quantum number (l) : orbital angular momentum, the shape of orbital Magnetic quantum number (m) : the direction of the angular momentum vector Spin quantum number (s) : intrinsic angular momentum of given particle

The Introduction of SPIN

Failure . Fine structure in spectral lines

The Bohr model of the hydrogen atom

. Fine structure in spectral lines

656.3nm
: Theoretical

: Experimental 0.14nm

 Failure

. Fine structure in the anomalous Zeeman effect

The nomal Zeeman effect

The anomalous Zeeman effect

The Introduction of SPIN

Samuel Goudsmit & George Uhlenbeck proposed in 1925; Every electron has an intrinsic angular momentum, called spin, whose magnitude is the same for all electrons. Associated with this angular momentum is a magnetic moment.

The Introduction of SPIN

Charged sphere spinning on its axis??

so small, many times greater than the velocity of light

Failure . Fine structure in spectral lines

The Bohr model of the hydrogen atom

. Fine structure in spectral lines

656.3nm
: Theoretical

: Experimental 0.14nm

Failure . Fine structure in the anomalous Zeeman effect

Anomalous Zeeman effect spin (splitting)

Samuel Goudsmit & George Uhlenbeck proposed in 1925; Every electron has an intrinsic angular momentum, called spin, whose magnitude is the same for all electrons. Associated with this angular momentum is a magnetic moment.

Charged sphere spinning on its axis??

so small, many times greater than the velocity of light

Magnetic moment
Usually, the net spin quantum number is 0. However, in the nuclei with odd mass number, net spin quantum number is half intiger.

Then, they produce magnetic momentum.

Spin angular momentum

Spin magnetic moment

In Large external magnet

In Large external magnet

Lamor Precession
H

d/dt = ( X H)
( )

, , d/dt = (H + ) . = H , d/dt = 0 . , H , H .

2 n(rad/sec) =
, , 2 = H

, = H / 2

Spin

Energy

Net magnetization rotates down to xy plane.

It will precess in xy plane.

Faradays Law of Induction

Fourier transform

 Magnetic resonance by nuclei Resonant absorption by nuclear spins will occur only when electromagnetic radiation of the correct frequency (e.g., equaling the Larmor precession rate) is being applied to match the energy difference between the nuclear spin levels in a constant magnetic field of the appropriate strength. The energy of an absorbed photon is then E = h0, where 0 is the resonance radiofrequency that has to match (that is, it has to be equal to) the Larmor precession frequency L of the nuclear magnetization in the constant magnetic field B0

Magnetic resonance by nuclei Resonant absorption by nuclear spins will occur only when electromagnetic radiation of the correct frequency (e.g., equaling the Larmor precession rate) is being applied to match the energy difference between the nuclear spin levels in a constant magnetic field of the appropriate strength. The energy of an absorbed photon is then E = h0, where 0 is the resonance radiofrequency that has to match (that is, it has to be equal to) the Larmor precession frequency L of the nuclear magnetization in the constant magnetic field B0

Chemical Shift

Chemical Shifts

NMR TMS NMR ppm ( scale).

*TMS(tetramethylsilane) NMR spectrum (0ppm) .

Chemical Shift
The surrounding electron shield the nuclear spins from the larger magnetic field. This result in a reduction in the energy spacing and a lower Lamor frequency.

Spin-Spin coupling

Spin-Spin Splitings
Spin-spin spliting . BrCH2CHBr2 . 1 (B0) () () . 2 B0 spin-spin spliting .

Spin-Spin Splitings

Spin-Spin Splitings

Spin-Spin Splitings
Intensity
One proton 1:1 Two equivalent protons 1:2:1 Three equivalent protons 1:3:3:1

Spin-spin spliting . BrCH2CHBr2 . 1 (B0) () () . 2 B0 spin-spin spliting .

 Intensity

One proton 1:1 Two equivalent protons 1:2:1 Three equivalent protons 1:3:3:1

Signal Number Chemical Proton Signal Location Proton Chemical Shift Signal Height signal Proton Ratio

Signal Splitting Proton

NMR signal Proton .

Proton NMR

Signal . (Ex : Diastereotopic)

Proton NMR Signal

. (Ex : Enantiotopic)

Signal , Chemical shift . NMR signal .

shielding Proton .
Proton shielding downfield .

Signal Proton .

C C Proton . 4 .

Proton . Ex : -NH, -OH Benzen Signal . ( Signal )

How to improve sensitivity