Spin Crossover of Thiophosgene via Multidimensional Heavy-Atom Quantum Tunneling

The spin-crossover reaction of thiophosgene has drawn broad attention from both experimenters and theoreticians as a prime example of radiationless intramolecular decay via intersystem crossing. Despite multiple attempts over 20 years, theoretical predictions have typically been orders of magnitude in error relative to the experimentally measured triplet lifetime. We address the T1 → S0 transition by the first application of semiclassical golden-rule instanton theory in conjunction with on-the-fly electronic-structure calculations based on multireference perturbation theory. Our first-principles approach provides excellent agreement with the experimental rates. This was only possible because instanton theory goes beyond previous methods by locating the optimal tunneling pathway in full dimensionality and thus captures “corner cutting” effects. Since the reaction is situated in the Marcus inverted regime, the tunneling mechanism can be interpreted in terms of two classical trajectories, one traveling forward and one backward in imaginary time, which are connected by particle–antiparticle creation and annihilation events. The calculated mechanism indicates that the spin crossover is sped up by many orders of magnitude due to multidimensional quantum tunneling of the carbon atom even at room temperature.