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Relaxation of a density or composition fluctuation involving many constituents. Its coefficient can depend on osmotic compressibility and collective mobility, and need not equal the tagged-particle self-diffusion coefficient at nonzero concentration.

John E. Tanner was a physical chemistry researcher whose work with Edward O. Stejskal established pulsed field gradient NMR as a method for measuring self-diffusion. He studied physical chemistry at Oberlin, Indiana and Wisconsin, and later worked at Idaho National Laboratory. His early NMR work received renewed recognition with an honorary fellowship in 2016.^[ref]

The appeal of pulsed field gradient NMR was practical as well as theoretical: strong magnetic field gradients could encode motion without remaining strong during excitation or detection. In a 2017 interview with Derek Jones, Tanner recalled choosing Stejskal's laboratory because it had a magnet and because he wanted to measure slow diffusion. He also described rebuilding the probe to deal with eddy currents generated by switching the magnetic field gradients.^[ref]

Tanner made restricted diffusion experimentally concrete. He described assembling 99 layers of mica with aluminium foil spacers, carefully removing wrinkles and burrs to obtain regular gaps. Such a controlled geometry lets an echo probe displacement between known barriers, rather than treating every loss of NMR signal as free diffusion with a smaller diffusion coefficient.^[ref]

His 1970 work used a stimulated echo to extend the observation interval when spin-lattice relaxation is slower than transverse relaxation. The interval can store the relevant pattern as longitudinal magnetization, rather than keeping it transverse throughout.^[ref] For an illustrative ideal comparison, take $T_1=1\mathrm{s}$, $T_2=0.1\mathrm{s}$ and storage time $T=0.5\mathrm{s}$. The storage-dependent nuclear spin relaxation factors are $e^{-T/T_1}\simeq 0.607$ and $e^{-T/T_2}\simeq 0.00674$. Even allowing the ideal three-pulse pathway's initial factor of $1/2$, the former factor is about 45 times larger. This compares only that storage contribution: pulse losses, the other transverse intervals and diffusion attenuation still matter.^[ref]

The Stokes–Einstein relation connects thermal diffusion with dissipative mobility. For a dilute suspension of isolated rigid spheres of hydrodynamic radius $a$ in an unbounded Newtonian fluid of viscosity $\eta$,where $\zeta$ is translational drag coefficient, $D$ diffusion coefficient and $T$ absolute temperature. Stokes drag supplies $\zeta =6\pi \eta a$ under no-slip, continuum, low-Reynolds-number conditions. The Einstein diffusion relation $D=k_{B}T/\zeta$ is more general than that particular spherical drag law.

A short equilibrium argument explains the connection. Let a weak external potential $U$ exert force $\mathbf{F}=-\nabla U$, so drift velocity is $\mathbf{F}/\zeta$. The number flux is $\mathbf{j}=n\mathbf{F}/\zeta -D\nabla n$. A Boltzmann distribution $n\propto e^{-U/(k_{B}T)}$ has $\nabla n=n\mathbf{F}/(k_{B}T)$; requiring zero equilibrium flux fixes $D=k_{B}T/\zeta$. thermal fluctuations and viscous dissipation are therefore linked, rather than independent adjustable effects. The original theory also relates diffusion to measured random displacements.^[ref]

On times long compared with momentum relaxation, an isotropic diffusing sphere hassingle-particle tracking can measure the slope. Alternatively, dilute single-scattering dynamic light scattering measures a field correlation $g_1(q,t)=e^{-D{q}^{2}t}$; the corresponding intensity-correlation excess is proportional to $e^{-2D{q}^{2}t}$. The scattering wavenumber and the distinction between field and intensity decay must be retained.

A Stokes-Einstein experimental consistency test independently measures temperature and solvent viscosity, uses a narrow distribution of inert spheres, checks decay rate proportional to $q^2$ or displacement variance proportional to time, and extrapolates toward infinite dilution. Subtract drift, account for wall-enhanced drag, and verify that aggregation is absent. Tracking additionally needs spatial calibration and correction for finite exposure and localization precision. At finite concentration, collective diffusion is not automatically the single-particle self-diffusion in the equation. A hydrodynamic radius is not generally identical to a polymer radius of gyration; nonspherical particles, slip or viscoelastic solvents require a different mobility model.

The Stejskal-Tanner equation relates diffusion-sensitive echo attenuation to a rectangular gradient-pair experiment:It assumes free Gaussian diffusion with a constant scalar diffusion coefficient $D$, ideal refocusing and two equal nonoverlapping rectangular gradient pulses of magnitude $g$ and duration $\delta$, whose starting times are separated by $\Delta$. The gyromagnetic ratio $\gamma$ is angular. The baseline $S_0$ is an otherwise matched echo without the applied diffusion-encoding gradients. These definitions are part of the formula, rather than optional choices of notation.^[ref]

The finite-duration term follows directly from the encoding history. Write $q_0=\gamma g\delta$. The effective encoding rises linearly from zero to $q_0$, stays constant for $\Delta -\delta$, then falls linearly to zero. Each ramp contributes $q_0^2\delta /3$ to the diffusion weighting b-value, soThe two physical gradients can have the same polarity: the intervening $180^{\circ }$ pulse reverses the effective phase-encoding sign.

For the illustrated $\delta =2\mathrm{ms}$ and $\Delta =30\mathrm{ms}$, the normalized integral $b/q_0^2$ is $29\frac{1}{3}\mathrm{ms}$, rather than $30\mathrm{ms}$. This isolates the pulse-duration correction without assigning an unmeasured gradient amplitude.

The 1965 work combined theory with apparatus tests, including slow self-diffusion in dry glycerol.^[ref] Restricted diffusion, flow, background gradients and measurement noise require their own interpretation; fitting a single attenuation to this equation does not establish all of its assumptions.