First principles calculations of Structure and electrostatic properties of non ligated CdSe nanoclusters

Abstract: Structural and charge relaxation of nanoclusters of CdSe of diameter 1-2 nm are studied with first principle calculations. The relaxations cause significant distortions of smaller systems of ~ 1 nm in diameter and have very minimal effect on the larger systems of ~ 2 nm in diameter. The Cd atoms are pulled in while the Se atoms are pulled out, which results in the flattening of Cd-terminated surface and retention of a zig-zag surface for Se-terminated surface. The surfaces terminated with both Cd and Se result in significant geometrical distortion resulting in charge concentrations at the distorted sites. The associated dipole and quadrupole moments are a function of the distortion or unequal distribution of Cd and Se. The HOMO and HOMO-1 orbitals are located on or near the distortions. Based on the tetrahedral coordination and robustness of the core structure to surface relaxation, the approx. 2 nm diameter NC is the best candidate for building macroscopic structures from NCs.