Which Is Better at Predicting Quantum-Tunneling Rates: Quantum Transition-State Theory or Free-Energy Instanton Theory?

Quantum transition-state theory (QTST) and free-energy instanton theory (FEIT) are two closely related methods for estimating the quantum rate coefficient from the free-energy at the reaction barrier. In calculations on one-dimensional models, FEIT typically gives closer agreement than QTST with the exact quantum results at all temperatures below the crossover to deep tunneling, suggesting that FEIT is a better approximation than QTST in this regime. Here we show that this simple trend does not hold for systems of greater dimensionality.

Shallow-tunnelling correction factor for use with Wigner-Eyring transition-state theory.

We obtain a shallow-tunnelling correction factor for use with Wigner-Eyring transition-state theory (TST). Our starting point is quantum transition state theory (QTST), which approximates the accurate quantum rate as the instantaneous flux through a delocalised transition-state ensemble of ring-polymers. Expanding the ring-polymer potential to second order gives the well-known Wigner tunnelling-factor which diverges at the cross-over temperature between deep and shallow tunnelling.

Enantioselective degradation, abiotic racemization, and chiral transformation of triadimefon in soils.

Triadimefon is a widely used triazole fungicide with one chiral carbon center. In soils, plants, and animals, triadimefon could be metabolized to triadimenol by reduction of the carbonyl group to an alcohol, resulting in the occurrence of a second chiral carbon in triadimenol. The enantioselective degradation of triadimefon and its chiral transformation to triadimenol in two soils, a Baoding alkaline yellow soil and a Wuhan acidic red soil, were investigated.