Take forward as increasing , and specify the sinusoidal amplitude convention by
Thus the unforced barrier is , not . Let and . Stationary points exist because . A minimum is at and its forward saddle at . The distances and activation barriers are
Use an Arrhenius estimate with the supplied distance-squared waiting-time scaling, . Calibrate at with and rate in each direction. At the explicit room-temperature estimate , , giving
Applying the same distance rule separately backwards gives and hence the literal scaling-model estimate
Thermodynamic qualification: for isothermal diffusion in this translated tilted potential, adjacent wells differ by , so local detailed balance instead requires . The two separate distance prefactors introduce an extra factor , inconsistent with that requirement. Keeping the forward estimate while enforcing the proper ratio gives
Both interpretations are shown because the supplied distance heuristic is not, by itself, a thermodynamically consistent prescription for both directional prefactors. Additional hidden chemical driving would require its own affinity, not an unexplained prefactor asymmetry. A common transition-state prefactor, as in a consistent Kramers model, preserves the Boltzmann rate ratio. Moreover the forward barrier is only about , so rare-escape exponential dwell kinetics and the numerical rate should be regarded as rough estimates. If “amplitude” meant the entire unforced barrier height, the maximum restoring force would be only and no dwell wells would survive at ; the amplitude convention is therefore essential.

Articles by others on the same topic (0)

There are currently no matching articles.