Ab initio finite field (hyper)polarizability computations on stoichiometric gallium arsenide clusters GanAsn (n=2-9).
We report reliable ab initio finite field (hyper)polarizability values at Hartree-Fock and second order Moller-Plesset perturbation theory (MP2) levels of theory for different geometrical configurations of small gallium arsenide clusters Ga(n)As(n) with n=2-5. We relied on all-electron basis sets and pseudopotentials suitable for (hyper)polarizability calculations. In each case, we used structures that have been established in the literature after we optimized their geometries at B3LYP/cc-pVTZ-PP level of theory. Our results suggest that the first order hyperpolarizability (beta) is much more sensitive to the special geometric features than the second order hyperpolarizability (gamma). For the most stable configurations up to ten atoms the second order hyperpolarizability at MP2 level of theory varies between 15 x 10(4) and 32 x 10(4) e(4)a0 (4)Eh(-3). In addition, we examined the polarizability per atom evolution versus the cluster size for Ga(n)As(n) with n=2-9. Our work extends earlier theoretical studies which were limited to eight atoms and exposes that the polarizability/atom of the most stable stoichiometric configurations up to Ga(9)As(9) continues the monotonic downward trend with increasing size. Lastly, from the methodological point of view, our analysis shows that apart from polarizabilities, augmented pseudopotentials yield reliable first and second hyperpolarizability values as well.
Karamanis
Panaghiotis
P
Institut Pluridisciplinaire en Recherche sur l'Environnement et les Matériaux, UMR 5254 CNRS, Equipe de Chimie Physique, Groupe de Chimie Théorique, IFR, Rue Jules Ferry, BP 27540, F-64075 PAU, Cedex, France.
Bégué
Didier
D
Pouchan
Claude
C