 Spectral diffusion

Spectral diffusion is the time-dependent wandering of a transition frequency as its local environment changes. A collection of molecules can retain the same instantaneous frequency distribution while individual members lose memory of their earlier frequencies. In the infrared spectroscopy setting, vibrational spectral diffusion concerns vibrational transitions. The name describes frequency evolution, not necessarily spatial diffusion of the molecules.

A useful original stationary model writes $\omega (t)=\overline{\omega }+\delta \omega (t)$ and defines the autocovariance functionFor a real stationary process, its frequency-increment variance isThis follows by expanding the square: stationarity makes the two squared-frequency terms equal, while the cross term is $2C(T)$. The relation supplies a spectral-diffusion frequency-increment variance without assuming that the mean transition frequency shifts.

Take the stipulated model $C(T)={\Delta }^2{e}^{-|T|/\tau }$, with $\Delta =1\mathrm{rad}\mathrm{p}{\mathrm{s}}^{-1}$ and $\tau =2\mathrm{ps}$. After 2 ps, normalized memory is $e^{-1}\approx 0.368$ and the root-mean-square frequency change is $\sqrt{2(1-e^{-1})}\approx 1.124\mathrm{rad}\mathrm{p}{\mathrm{s}}^{-1}$. The long-time increment spread approaches $\sqrt{2}\Delta$, while the single-time spread remains $\Delta$. Thus loss of temporal correlation need not broaden the stationary ensemble distribution over time.

A static distribution offers a contrasting physical limit. Molecules may have different, but individually fixed, frequencies. Then $C(T)=C(0)$ and the increment variance is zero despite a broad ensemble spectrum. A single spectral line width cannot determine how much of that diversity is static or dynamically sampled.

In two-dimensional infrared spectroscopy, controlled infrared pulses first label frequency and later interrogate the response after a 2D IR waiting time. Repeating over waiting times tests the frequency relation rather than merely measuring one ensemble average.^[ref] Its calculated spectra illustrate the associated evolution of spectral geometry.^[ref]

Environmental fluctuations, population loss and exchange between resolved species affect spectra in different ways. A changing 2D IR line-shape correlation is useful evidence only with an appropriate response model and controls. A fitted time scale is not automatically a molecular transport coefficient or the lifetime of every environmental structure.