Effect of the cluster size in modeling the H_2 desorption and dissociative adsorption on Si(001)

TL;DR

This study investigates how the size of silicon clusters affects the accuracy of modeling hydrogen desorption and dissociation on Si(001) surfaces, comparing cluster models with slab calculations to determine the most reliable approach.

Contribution

It systematically evaluates the impact of cluster size on reaction energetics, highlighting that larger clusters like Si_21H_20 better approximate slab results for Si(001).

Findings

Smaller clusters overestimate activation barriers.

Si_21H_20 cluster predicts reaction energetics close to slab calculations.

Differences in activation energies are linked to cluster size and surface property representation.

Abstract

Three different clusters, Si_9H_12, Si_15H_16, and Si_21H_20, are used in density-functional theory calculations in conjunction with ab initio pseudopotentials to study how the energetics of H_2 dissociativ e adsorption on and associative desorption from Si(001) depends on the cluster size. The results are compared to five-layer slab calculations using the same pseudopotentials and high qu ality plane-wave basis set. Several exchange-correlation functionals are employed. Our analysis suggests that the smaller clusters generally overestimate the activation barriers and reaction energy. The Si_21H_20 cluster, however, is found to predict reaction energetics, with E_{a}^{des}=56 +- 3 kcal/mol (2.4 +- 0.1 eV), reasonably close (though still different) to that obtained from the slab calculations. Differences in the calculated activation energies are discussed in relation to the efficiency of clusters to describe the properties of the clean Si(001)-2x1 surface.