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. Here, we show how to remove this divergence by integrating numerically over the two softest ring-polymer normal modes. This results in a modified Wigner correction factor involving a one-dimensional integral evaluated along a straight line on the potential energy surface. Comparisons with accurate quantum calculations indicate that the newly derived correction factor gives realistic estimates of quantum rate coefficients in the shallow-tunnelling regime.

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. We report tests on several collinear and three-dimensional reactions, in which QTST outperforms FEIT over a range of temperatures below crossover, which can extend down to half the crossover temperature (below which FEIT outperforms QTST). This suggests that QTST-based methods such as ring-polymer molecular dynamics (RPMD) may often give closer agreement with the exact quantum results than FEIT.

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. The results showed the occurrence of enantioselectivity with R-(-)-triadimefon preferentially degraded in both soils. Abiotic racemization was observed by incubation of enantiopure triadimefon enantiomers. The racemization was clearly pH dependent and took place much more rapidly in Baoding alkaline soil than in Wuhan acidic soil. Further enantioselective analysis of converted triadimenol showed that triadimenol stereoisomer concentration invariably followed the order 1R,2R>1S,2S>1S,2R>1R,2S in Baoding soil, regardless of racemic triadimefon or single enantiomers initially treated. However, in the case of Wuhan soil, different triadimenol stereoisomer patterns could be produced depending on initial triadimefon composition at the time of application. The abiotic racemization was documented to have a great influence on the chiral profiles of triadimefon and its metabolite triadimenol. The mechanism and structural consideration of the racemization were further discussed, underscoring the importance of considering configurational stability in proper evaluation of environmental fate and risk of chiral pesticides.