Theoretical and Computational Chemistry

Heavy-Atom Quantum Tunnelling in Spin Crossovers of Nitrenes



We simulate two recent matrix-isolation experiments at cryogenic temperatures, in which a nitrene undergoes spin crossover from its triplet state to a singlet state via quantum tunnelling. We detail the failure of the commonly applied weak-coupling method (based on a linear approximation of the potentials) in describing these deep-tunnelling reactions. The more rigorous approach of semiclassical golden-rule instanton theory in conjunction with double-hybrid density-functional theory and multireference perturbation theory does, however, provide rates and kinetic isotope effects in good agreement with experiment. In addition, these calculations locate the optimal tunnelling pathways, which provide a molecular picture of the reaction mechanism. The reactions involve substantial heavy-atom quantum tunnelling of carbon, nitrogen and oxygen atoms, which unexpectedly even continues to play a role at room temperature.


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Supplementary material

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Supporting Information
The supporting information includes further details on the electronic-structure methodology and rate calculations.