Timescale prediction of complex multi-barrier pathways using flux sampling molecular dynamics and 1D kinetic integration: Application to cellulose dehydration

Abstract

Reactive molecular dynamics (MD) simulations, especially those employing acceleration techniques, can provide useful insights on the mechanism underlying the transformation of buried organic matter, yet, so far, it remains extremely difficult to predict the time scales associated with these processes at moderate temperatures (i.e., when such time scales are considerably larger than those accessible to MD). We propose here an accelerated method based on flux sampling and kinetic integration along a 1D order parameter that can considerably extend the accessible time scales. We demonstrate the utility of this technique in an application to the dehydration of crystalline cellulose at temperatures ranging from 1900 K to 1500 K. The full decomposition is obtained at all temperatures apart from T = 1500 K, showing the same distribution of the main volatiles (H2O, CO, and CO2) as recently obtained using replica exchange molecular dynamics. The kinetics of the process is well fitted with an Arrhenius law with Ea = 93 kcal/mol and k0 = 9 × 1019 s-1, which are somehow larger than experimental reports. Unexpectedly, the process seems to considerably slow down at lower temperatures, severely departing from the Arrhenius regime, probably because of an inadequate choice of the order parameter. Nevertheless, we show that the proposed method allows considerable time sampling at low temperatures compared to conventional MD.