Coherent rotational tunneling and incoherent dynamics in aD 2 D 2 solid non-classical complex studied by 2 H solid state NMRRuD 2 spectroscopy

The 2H solid state NMR spectra and relaxation data of a transition metal g2-dideuterium complex, namely 1 have been measured in the temperature regime from 5.4 to 320 K. 2222226 , In the sample, coherent and incoherent exchange processes on the time scale of the quadrupolar 2 interaction have been found, leading at low temperatures to a tunnel splitting of the 2H NMR spectrum. With increasing temperature a slight increase of the tunnel splitting is observed, in conjunction with a strong increase of the incoherent exchange process, which Ðnally, at temperatures above 20 K, destroys the tunnel splitting and determines the spectral line shape. For the description of the experimental spectra a Liouville formulation of the AlexanderÈBinsch NMR line shape theory, adapted for exchanging deuterons, is employed. It is shown that the whole evaluation of the 2H magnetization takes place in four 2D and two 4D subspaces of the 81D Liouville space, leading to a drastic simpliÐcation of the numerical e†orts in the simulation of the spectral line shapes. The height of the tunnel barrier calculated from the value of the tunnel splitting is 270 meV (6.22 kcal mol~1). The incoherent exchange rates extracted from the spectra and from relaxation data 1 are analyzed in terms of a Bell tunneling model, with a temperature dependent e†ective potential.