Estudo de nanofios metálicos por primeiros principios

Abstract

In the present work, we investigate electronic and structural properties of nanowires based on noble metals (Au,Ag,Pt,Pd) and mid-series 4d and 5d transition metals (W,Mo,Ta,Nb). We employ an ab initio methodology implemented in the SIESTA package, based in theKohn-Sham formulation of density functional theory (DFT). The generalized gradient approximation (GGA) is used for the exchange- correlation energy and pseudopotentials are used in order to reduce computational cost. In the second chapter we give a brief description of the methodology used in calculations. In the third chapter we study theimpact of the relativistic effect in linear and zigzag chains made of noble metals and mid-series transition metals. In the noble metals the relativistic effect tends to favor energetically the low coordination structures. This effect is stronger in the 5d metals where the atomic number Z is larger. As a consequence, the relativistic effect stabilizea two-fold coordinated structure in the 5d noble metals which is not stable in the 4d noble metals. In the case of the mid-series transition metals the relativistic effect has the opposity effect, i.e., it tends to destabilize the low coordination structures. The relativistic effect causes a contraction in the low coordination bonds in the noble metals and causesan expansion in the case of the middle series transition metals. In the fourth chapter we study ultrathin nanowires made of Au, Ag and of the Au-Ag alloy. The linear atomic densities of these ultrathin nanowires are restricted to a range of 0.7 to 1.0 atoms/°A. We introduce in this work a new geometry that our calculations indicate to be more stable than the previously geometries for these systems, by about 0.1 eV/atom. This structure is insulating for both metals and for related Au0.5-Ag0.5 alloys, with gaps of 1.3 eV for Au, o.8 eV for Ag, and varying between 0.1 eV and 1.9 eV for the alloys. In the fifth chapter we investigate electronic and structural properties of nanowires and nanotubes made of Au and Ag with linear atomic densities in a range of 1.1 to 5.1 atoms/°A. We study the stability of the nanowires and nanotubes as a function of the their respectives linear atomic densities. We observe from the calculations that the relativistic effects tends to turn the nanotubes more competitive energetically with the fcc based structures nanowires. As this effect is stronger in Au than Ag it happens that nanotubes are more competitiveswith the fcc nanowires in Au than in Ag. In this work we propose a deformation of the non-quiral (2n, n) nanotubes of Ag and Au that lowers the energy of the nanotube. This deformation consists of a flattening of the nanotube wall, that icreases the aspect ratio of the resulting structure. We calculate the energy barrier involved in the transformation of the (10, 5) tube into the distored flatterned one, and we observe that the (10, 5) tube is unstable for temperatures above 40 K.