# Gold Nanowires and their Chemical Modifications

## Abstract

Equilibrium structure, local densities of states, and electronic transport in a gold nanowire made of a four-atom chain supported by two gold electrodes, which has been imaged recently by high-resolution electron microscopy, and chemical modification of the wire via the adsorption of a methylthiol molecule, are investigated with ab-initio local density functional simulations. In the bare wire at the imaged geometry the middle two atoms dimerize, and the structure is strongly modified by the adsorption of the molecule with an accompanying increase of the ballistic conductance through the wire.

PACS: 73.40.Jn, 73.61.-r, 85.30.Vw

Generation of wires of atomic scale dimensions in the process of formation and/or elongation of interfacial contacts has been predicted through early molecular dynamics simulations using many-body potentials , and in the face of fundamental interest and technological considerations driven by the relentless miniaturization of electronic and mechanical devices such wires have been the subject of intensive experimental and theoretical research endeavors . Indeed, nanometer-scale wires (nanowires, NWs) have been created and their structural, mechanical, and transport characteristics were studied using a variety of techniques , including most recently combined scanning tunneling microscopy (STM) and direct imaging with the use of high-resolution transmission electron microscopy (HRTEM) .

We report here on ab-initio local-density functional (LDA) investigations  of the atomic structure, electronic spectrum and conductance of a gold NW consisting of a four-atom chain connected to gold electrodes, which is the smallest NW imaged by HRTEM . Our study reveals dimerization of the gold atoms in the middle of the chain  akin to a Peierls transition in (extended) one-dimensional systems. Furthermore, we explore structural and electronic spectral modifications resulting from adsorption of a molecule (methylthiol, SCH<sub>3</sub>) to the wire , demonstrating the sensitivity of these properties to such chemical interactions, as well as their effect on the electronic conductance of the wire which we find to increase upon adsorption. These results provide a new interpretation of the measured HRTEM image of the atomic gold wire  and suggest a new strategy for formation of organo-metallic NWs, as well as the use of NWs as monitoring and chemical sensing devices.

In light of the aforementioned STM/HRTEM observations  we start our simulation from a 4-atom Au wire consisting of two tip-atoms (t) located at the apexes of two opposing tip-electrodes distanced initially by $`d_{tt}^{(0)}`$=8.9 Å, and of two internal Au atoms (i) located in the gap between the two electrodes with initial uniform distances $`d_{ti}^{(0)}`$=$`d_{ii}^{(0)}`$=2.967 Å between neighboring atoms of the wire; the tip-electrodes consist each of 29 gold atoms arranged in a pyramidal shape made of face-centered-cubic stacked (110) layers and exposing (100) and (111) facets, with the tip atoms (as well as the internal wire atoms) and the atoms of the underlying layers supporting them treated dynamically, while the rest of the electrode gold atoms are held at their crystalline lattice positions. This initial structure relaxes spontaneously in the course of a total energy minimization with a 0.16 eV gain in the total energy, to that shown in Fig. 1 (AuNW, left) where the two inner wire atoms dimerize, with $`d_{ii}`$=2.68 Å (compared to $`d`$(Au-Au)=2.48 Å in a free Au<sub>2</sub> molecule), $`d_{ti}`$=3.07 Å, and the total length of the wire shortens to $`d_{tt}`$=8.82 Å (see ref. ).

From the local density of states (LDOS) of the dimerized wire (Fig. 2), calculated in the regions delineated in Fig. 1 (AuNW, left), we observe that the electronic states in the interior region of the wire (region E, see Fig. 1, left) near the Fermi energy ($`E_F`$, marked by a dashed line in Fig. 2) are not found in the free Au<sub>2</sub> dimer (whose states are marked by dots on the upper energy axis of Fig. 2). Rather, these states originate from hybridization between the atomic states of the interior Au atoms and the gold-electrode states, with the highest-occupied molecular orbital (HOMO) exhibiting a dominant d-character on the interior wire atoms. The dimerization is driven by lowering of the energies of states in the interval $`10E6.5`$ eV calculated at the interior region of the wire (compare the upper and and lower LDOS curves in the inset to Fig. 2, corresponding to the dimerized and initial equal-distance configurations, respectively). Additionally, the dimerization of the wire is accompanied by a small increase of the energy gap near $`E_F`$ from 0.194 eV in the equidistant wire to 0.216 eV in the dimerized one; in a certain sense the observed dimerization may be regarded as a ”predecessor” of a Peierls transition, though such description should be treated with caution due to the rather limited extent of the wire considered here. The calculated electronic conductance  of the dimerized AuNW is $`G`$=0.58 $`g_0`$ ($`g_0`$=$`2e^2/h`$, where $`e`$ is the electron charge and $`h`$ is the Planck constant) corresponding to a resistance of 22.17 k$`\mathrm{\Omega }`$, and ballistic transport occurs through a single conductance channel .

Two binding configurations of a methylthiol molecule to the dimerized equilibrium configuration of the AuNW were considered: (i) the SCH<sub>3</sub> molecule bonded to the two middle interior Au atoms of the wire (see AuNW/m-SCH<sub>3</sub> in Fig. 1), and (ii) binding of the molecule to a terminal tip atom (t) of the wire and to the neighboring interior wire atom (see AuNW/t-SCH<sub>3</sub> in Fig. 1). The binding energies of the molecule in the two adsorption configurations are essentially the same (4.01 eV), and in both cases binding of the molecule is accompanied by significant structural changes of the wire. In the m-SCH<sub>3</sub> configuration (Fig. 1, middle) the dimerization of the interior wire gold atoms is removed, and the sulfur atom is bonded to the two interior gold atoms with $`d`$(S-Au)=2.31 Å, the angle $`\mathrm{}`$(Au-S-Au)=117.4<sup>o</sup>, and $`d`$(S-C)=1.84 Å. The configuration is symmetric about a plane of reflection passing through the sulfur atom normal to the plane of the figure, and the length of the wire increases by 0.1 Å (i.e., $`d_{tt}`$=9.02 Å), with $`d_{ti}`$=2.58 Å and $`d_{ii}`$=3.94 Å; the wire atoms are shifted slightly in the direction of the adsorbed molecule with the terminal wire atoms displaced laterally by 0.016 Å from the four-fold hollow site of the underlying gold electrode layer. Dimerization of the interior gold wire atoms is removed also in the t-SCH<sub>3</sub> equilibrium bonding configuration where symmetry is broken, the bond lengths of the sulfur to the two gold atoms are unequal \[$`d`$(S-Au(t))=2.38 Å and $`d`$(S-Au(i))=2.31 Å\], the angle $`\mathrm{}`$(Au(t)-S-Au(i))=109.3<sup>o</sup>, $`d_{ti}`$=3.83 Å, $`d`$(S-C)=1.85 Å, and the length of the wire is $`d_{tt}`$=8.98 Å; additionally, the Au(t) atom bonded to the sulfur is displaced laterally by 0.057 Å from the four-fold hollow site, while the displacement of the other Au(t) atom (not bonded directly to the molecule) is 0.012 Å. We remark that in both adsorption configurations the intra-thiol $`d`$(S-C) distance, as well as the S-Au bond length are similar to those calculated for the equilibrium structure of a free Au<sub>2</sub>SCH<sub>3</sub> molecule where $`d`$(S-C)=1.84 Å and $`d`$(S-Au)=2.41 Å, while the Au-S-Au angles in the thiolated wires are much larger than in the free molecule (where $`\mathrm{}`$(Au-S-Au)=67.1<sup>o</sup>) due to the binding of the sulfur-bonded gold atoms of the wire to the rest of the nanostructure.

Examination of the LDOS for the chemically modified wires displayed in Fig. 3 reveals that changes from the spectrum of the bare dimerized wire (Fig. 2) are localized to regions in the immediate vicinity of the molecular binding site (compare region E in Fig. 2 with region T for AuNW/m-SCH<sub>3</sub> and regions T and E’ for AuNW/t-SCH<sub>3</sub> in Fig. 3). In both cases $`E_F`$ lies below the HOMO level of the free SCH<sub>3</sub> molecule correlating with energy gain due to hybridization of the molecular states with the states of the wire. In both of the chemically modified wires the HOMO level is partially occupied (containing about one hole) while it is doubly occupied in the bare AuNW, and the gap between that level and the lowest unoccupied one is 0.21 eV and 0.316 eV in the m-SCH<sub>3</sub> and t-SCH<sub>3</sub>, respectively.

Chemical modifications of the AuNW are signaled, and may be detected, by changes in the electronic conductance, which increases upon adsorption, i.e. $`G`$(AuNW/m-SCH<sub>3</sub>)=0.82 $`g_0`$ and $`G`$(AuNW/t-SCH<sub>3</sub>)=0.88 $`g_0`$, involving a single conductance channel. While at first sight an increase of the conductance in the presence of an adsorbate may seem surprising, it can be explained via examination of the potential landscapes governing the propagation of the electron through the wires (see Fig. 4). Comparison between the potential shown in Fig. 4a for the bare dimerized nanowire with those corresponding to the chemically modified ones (Fig. 4b and 4c), reveals that the potential barriers (bottle-necks), associated with the unequal spacings between the gold atoms in the dimerized equilibrium structure and the reduced overlap between the electronic states of the inner wire and the tip atoms, which decrease the transmission of the incident electron through the bare AuNW (Fig. 4a), are reduced in the chemically modified wires and the conductance path is broadened, resulting in enhancement of the ballistic transmission through these wires .

These findings, obtained through ab-initio simulations, pertaining to the dimerized structure of an atomic gold nanowire and the sensitivity of structural, electronic, and conductance properties of such wires to chemical modifications via molecular adsorption, provide a new interpretation of recent HRTEM measurements , demonstrate methods for probing the nature of chemical interactions with such nanostructures, and suggest a strategy for preparation of chemically modified nanowires.

Acknowledgement. We thank A.G. Scherbakov for his assistance in conductance calculations. This research is supported by the U.S. DOE, AFOSR, and the Academy of Finland. Calculations were performed on an IBM SP2 parallel computer at the Georgia Tech Center for Computational Materials Science, and on a Cray T3E at the National Energy Research Scientific Computing Center (NERSC) at Berkeley, CA.