3.

NMR Relaxation Times T1 and T2

Brain Tumor in NMR images:

T1-weighted
(long T1
appears
darker

T2-weighted
T1-weighted with
long T2 appears paramagnetic
brighter
contrast agent

MRI of the brain showing

plaques in multiple
sclerosis disease

3. NMR Relaxation Times T1 and T2

Reminder 1:
Spin-Lattice Relaxation Time (longitudinal relaxation time) T1:
Recovery of z-magnetization into thermal equilibrium by energy
exchange between the (magnetic) spin system and the environment
(lattice)

Reminder 2:
Spin-Spin Relaxation Time (transversal relaxation time) T2:
Decay of x,y-magnetization to zero (into thermal equilibrium) by
energy exchange within the (magnetic) spin system

Problem:
What are the physics mechanisms behind those relaxation
processes?

Introduction

In a quantum mechanical two-level system exist two possible

transition mechanisms:
- Spontaneous transitions
- Stimulated transitions
Spontaneous emissions occur without prior absorption of a photon.
Stimulated transitions occur by absorption or emission of radiation.
The probability of stimulated transition is higher at lower energy gaps.
NMR is the area of stimulated transition.

It follows:
NMR transitions can be stimulated due to oscillating (magnetic) fields
of the correct resonance frequency and due to magnetic oscillations
in the environment

T1 relaxation describes the change of z-magnetization.

The whole energy E of the spin system in a magnetic field B ist:
E = MB = Mz B

During T1 relaxation the total energy E is changed

T2 relaxation describes the coherent transitions between energy
states without energy loss.

Two examples:
- Different local magnetic fields give different resonance
frequencies and therefore induce a phase distribution of the spins
in the rotating frame
- Other spins precess in the neighborhood at the correct resonance
frequency but at different phases, which stimulates transitions

In (almost) all cases:

T1 T2

Basic Physics of NMR Relaxation

-

Magnetic dipole-dipole interactions between spins

Thermal motion of molecules (and spins)

The motion is described using a characteristic correlation time c

c is the mean time for a molecule to travel the distance of its diameter
(translation), or fully rotate around itself (rotation)
A few examples:
c of a water molecule:
free in bulk water:
in hydrate shell:
in solid state (ice):

10-12 s
10-8 s
10-6 s

Isotropic statistic motion:

Autocorrelation function G(t):
(Means: after a few c there is no more information about the initial states)

After Fourier transformation, we get the

frequency distribution J() of the molecular motion:

Solid state

Viscous media
Liquid state

NMR resonance frequency

Depending on the NMR resonance frequency

(or magnetic field strength):
At solid state:
There are almost no (motional) frequency components in the region
of the NMR resonance frequency
At liquid state:
There are always (motional) frequency components in the region of
the NMR resonance frequency

If c is long and is low, the spins are for a longer time interval
in direct (magnetic) contact, which leads to a shorter T2 value
(more spin dephasing).
Schematic diagram:

Liquid state

Solid state

T1 is shortest, when the motional frequency is comparable to the

NMR resonance frequency (stimulated transition due to lattice
vibrations)
Schematic diagram:

Solid state
Liquid
state

The full theory is described in the BPP-Theory

(Bloch-Purcell-Pound)

with:
and is the
NMR resonance
frequency

A few results:
In the gas phase: very long T1 and T2 values (several hours or days!)
(due to large distances of the spins: r6 dependence!)
In the solid state: long T1 and very short T2 values (large difference!)

In the liquid state: long T1 and long T2 values (small differences!)

In viscous media: medium long T1 and T2 values (small and large
differences depending on resonance frequency)
T2 is (almost) not dependent on the field strength
T1 increases with increasing magnetic field strength
Differences in T1 values are smaller in high magnetic field strength,
especially in viscous media

Typical values of 1H NMR signals of water and lipid molecules in

biological tissue:
T1 :
T2 :

50 ms 5000 ms
1 ms 1000 ms

Additional NMR relaxation mechanisms:

1. Anisotropic chemical shift:
electronic shell in the molecules introduce additional
inhomogeneous magnetic fields, resulting in NMR line
broadening: 1/T1,2 ~ B02
2. Paramagnetic relaxation:
Single electrons (transition metal complexes or radicals)
have a 1000-times higher magnetic dipole moment
compared to nuclei and with 1/T1,2 ~ 2 have a 106-times
more efficient dipole-dipole-interaction.
Paramagnetic substances shorten especially T1
(e.g.: O2, Cu, Mn, Gd, Eu, .)
Used as NMR imaging contrast media

3. Magnetic particles:
Induce additional magnetic field inhomogeneities and
reduce especially T2
Used as NMR imaging contrast media

4. Quadrupolar relaxation:
Nuclei having a spin I > have an additional electrical
quadrupolar moment which interact with oscillating
electrical field gradients
Those nuclei (e.g. 23Na, etc.) have short T1,2 values

NMR relaxation times in biological tissue

(1H NMR signal of water and fat)
Large differences of T1 and T2 in soft tissue
(gives the basis of soft tissue contrast in NMR imaging)
Very short T2 values in hard tissue (bones, tendons, )
(bones, etc. not visible in NMR imaging)
NMR relaxation times are changed in diseases (infarct, tumor,
inflamation, )
NMR relaxation times can be changed using NMR contrast media
(magnetic nanoparticles, paramagnetic substances)

The quantitative interpretation of NMR relaxation times in biological

tissue remains difficult and is unsolved at the moment
Interesting area of research !

For practical NMR experiments:

T1 should be as short as possible:
T2 should be as long as possible:

Why?
Why?

There exists another relaxation time:

The effective T2:
T2*
This is the time constant describing the relaxation of the free
induction decay (The NMR-signal!).
T2* is always shorter than T2 and influenced by the magnetic
field inhomogeneity B, with:

1
1
= + B
T2 T2

1H

NMR relaxation times of water in biological tissue:

Water is distributed between different phases (i)

(free, bound water and water in hydration shells)
having different c and different T1,2,i
If the exchange rate of water is slow,
multiexponential relaxation behaviour will be detected
(with Pi: number of water molecules in different phases i):
M t =

Pi

t T
1,2,i
e

If the exchange rate is fast, a monoexponential relaxation is observed

with the weighted relaxation rate:
1
=
T1,2

Pi
i

T1,2,i