Shallow-tunnelling correction factor for use with Wigner–Eyring transition-state theory
文献情報
Yanchuan Zhang, Judith B. Rommel, Marko T. Cvitaš, Stuart C. Althorpe
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.
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