Shake-Rattle-and-Roll: A Model of Dynamic Structural Disorder in Supported Nanoscale Catalysts

TL;DR

This paper explores how dynamic structural disorder in supported nanoscale catalysts influences their behavior and reactivity, using a combination of statistical mechanics, simulations, and models to understand fluctuations and their effects.

Contribution

It introduces a novel approach combining statistical mechanics and real-time simulations to model dynamic structural disorder in nanoscale catalysts.

Findings

DSD causes significant fluctuations in energy and charge.

Dynamically sampled clusters show altered reaction barriers.

Catalytic activity is strongly affected by DSD.

Abstract

We investigate the effects of "dynamic structural disorder" (DSD) on the behavior of supported nano-scale catalysts. DSD refers to the intrinsic fluctuating, inhomogeneous structure of such nano-scale systems. In contrast to bulk materials, nano-scale systems exhibit substantial fluctuations in energy, charge, and other extensive quantities as well as large surface effects. The DSD is driven by the stochastic librational motion of the center of mass and fluxional bonding at the nanoparticle surface due to thermal coupling with the substrate. Our approach for calculating DSD is based on a combination of statistical mechanics, transient coupled-oscillator models, and real-time DFT/MD simulations. This approach treats thermal and dynamic effects over multiple time-scales, including bond-stretching and -bending vibrations, DSD, and transient tethering to the substrate at longer ps time-scales. Model calculations of molecule-cluster interactions and molecular dissociation reaction paths are presented in which the reactant molecules are adsorbed on the surface of dynamically sampled clusters. This model suggests that DSD affects both the prefactors and distribution of energy barriers in reaction rates, and thus can strongly affect catalytic activity at the nano-scale.