Oxygen impact on quantum confinement effect for silicon clusters in different size regimes: ab initio investigations

The phenomena where the parameter like optical gap, HOMO-LUMO gap etc of a cluster will behave like a monotonic function with respect to its size is called quantum confinement effect. Here we are dealing with clusters having number of silicon atoms as 10, 16, 19, 20, 35, 54 and 78 which are representatives of different size regime clusters. For each clusters we have experimented with a number of isomers and the results we are showing are only of the stable most isomers. Then for each clusters we are capping them with oxygen atoms and calculating their optical response using DFT based calculations. We also calculate their HOMO-LUMO gap with and without oxygen atoms. The main essence of this work is mainly revolving around the variation of optical gap as well as the HOMO-LUMO gap for all the clusters with respect to their size and also whether oxygen insertion can induce any changes in quantum confinement effect. Also for Si₂₀, Si₁₉, Si₁₆ and Si₁₀ we have calculating the optical spectra with a variation of inserted oxygen on the surface of those clusters. All the calculation are performed using Vienna ab initio simulation package (VASP) and Car Parrinello molecular dynamics (CPMD) for geometry optimization. The optical spectra of the clusters are performed by real space PARSEC code and time dependent density functional theory implemented RGWBS code which takes into account the many body effects using GW and BSE equations.