Dynamic NMR spectrum

Fluxional molecules are molecules that undergo dynamics such that some or all of their atoms interchange between symmetry-equivalent positions. Because virtually all molecules are fluxional in some respects, e.g. bond rotations in most organic compounds, the term fluxional depends on the context and the method used to assess the dynamics. Often, a molecule is considered fluxional if its spectroscopic signature exhibits line-broadening (beyond that dictated by the Heisenberg uncertainty principle) due to chemical exchange. In some cases, where the rates are slow, fluxionality is not detected spectroscopically, but by isotopic labeling.

The prototypical fluxional molecule is phosphorus pentafluoride. Its ¹⁹F NMR spectrum consists of a ³¹P-coupled doublet, indicating that the equatorial and axial fluorine centers interchange rapidly on the NMR timescale. Fluorine-19 NMR spectroscopy, even at temperatures as low as −100 °C, fails to distinguish the axial from the equatorial fluorine environments. The apparent equivalency arises from the low barrier for pseudorotation via the Berry mechanism, by which the axial and equatorial fluorine atoms rapidly exchange positions.

A well studied fluxional ion is the carbonium ion, which is protonated methane, CH₅⁺. In this unusual species, whose IR spectrum was recently experimentally observed and more recently understood, the barriers to proton exchange are lower than the zero point energy. Thus, even at absolute zero there is no rigid molecular structure, the H atoms are always in motion. More precisely, the spatial distribution of protons in CH₅⁺ is many times broader than its parent molecule CH₄, methane.

Temperature dependent changes in the NMR spectra result from dynamics associated with the fluxional molecules when those dynamics proceed at rates comparable to the frequency differences observed by NMR. The experiment is called DNMR and typically involves recording spectra at various temperatures. In the ideal case, low temperature spectra can be assigned to the "slow exchange limit", whereas spectra recorded at higher temperatures correspond to molecules at "fast exchange limit". Typically, high temperature spectra are simpler than those recorded at low temperatures, since at high temperatures, equivalent sites are averaged out. Prior to the advent of DNMR, kinetics of reactions were measured on nonequilibrium mixtures, monitoring the approach to equilibrium.

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