Molecular dynamics of adsorption and segregation from an alkane mixture.

Adsorption and segregation of n-hexadecane molecules from an equal by weight mixture of n-hexadecane and n-hexane to an Au(001) surface at 315 kelvin are studied with the use of molecular dynamics simulations. Preferential adsorption of n-hexadecane at the solid-to-liquid interface together with subsequent layer-by-layer growth of an ordered, wetting interface were observed. The long chains penetrate and adsorb at the interfacial layer by means of a sequential segmental mechanism involving end-segment anchoring and displacive desorption of preadsorbed n-hexane molecules.

Controlled deposition, soft landing, and glass formation in nanocluster-surface collisions.

Molecular dynamics simulations have been used to investigate the dynamics and redistribution of energy during the impact of a nanocrystal with adsorbed liquid films. Although impact of a 32-molecule NaCl cluster on a solid surface at 3 kilometers per second leads to melting, disordering, fragmentation, and rebounding, the same size cluster colliding with a liquid neon film transfers its energy efficiently to the liquid for a controlled soft landing. Impact on a higher density film (argon) leads to rapid attenuation of the cluster velocity, accompanied by fast heating. Subsequent disordering, melting, and fast cooling by evaporation of argon quench the cluster to a glassy state. These results suggest a method for the controlled growth of nanophase materials.

Dynamics of cluster-surface collisions.

The structure, energetics, and dynamics of shock conditions generated in a nano-cluster upon impact on a crystalline surface are investigated with molecular-dynamics simulations for a 561-atom argon cluster incident with a velocity of 3 kilometers per second onto a sodium chloride surface. The "piling-up" shock phenomenon occurring upon impact, coupled with cascades of energy and momentum transfer processes and inertial confinement of material in the interior of the cluster, creates a transient medium lasting for about a picosecond and characterized by extreme local density, pressure, and kinetic temperature. The nano-shock conditions and impulsive nature of interactions in the newly formed compressed nonequilibrium environment open avenues for studying chemical reactivity and dynamics catalysed via cluster impact.

Charge migration in DNA: ion-gated transport.

Electron hole (radical cation) migration in DNA, where the quantum transport of an injected charge is gated in a correlated manner by the thermal motions of the hydrated counterions, is described here. Classical molecular dynamics simulations in conjunction with large-scale first-principles electronic structure calculations reveal that different counterion configurations lead to formation of states characterized by varying spatial distributions and degrees of charge localization. Stochastic dynamic fluctuations between such ionic configurations can induce correlated changes in the spatial distribution of the hole, with concomitant transport along the DNA double helix. Comparative ultraviolet light-induced cleavage experiments on native B DNA oligomers and on ones modified to contain counterion (Na(+))-starved bridges between damage-susceptible hole-trapping sites called GG steps show in the latter a reduction in damage at the distal step. This reduction indicates a reduced mobility of the hole across the modified bridge as predicted theoretically.

Atomistic mechanisms and dynamics of adhesion, nanoindentation, and fracture.

Molecular dynamics simulations and atomic force microscopy are used to investigate the atomistic mechanisms of adhesion, contact formation, nanoindentation, separation, and fracture that occur when a nickel tip interacts with a gold surface. The theoretically predicted and experimentally measured hysteresis in the force versus tip-to-sample distance relationship, found upon approach and subsequent separation of the tip from the sample, is related to inelastic deformation of the sample surface characterized by adhesion of gold atoms to the nickel tip and formation of a connective neck of atoms. At small tipsample distances, mechanical instability causes the tip and surface to jump-to-contact, which in turn leads to adhesion-induced wetting of the nickel tip by gold atoms. Subsequent indentation of the substrate results in the onset of plastic deformation of the gold surface. The atomic-scale mechanisms underlying the formation and elongation of a connective neck, which forms upon separation, consist of structural transformations involving elastic and yielding stages.

Properties of metallic nanowires: from conductance quantization to localization.

Material structures of reduced dimensions exhibit electrical and mechanical properties different from those in the bulk. Measurements of room-temperature electronic transport in pulled metallic nanowires are presented, demonstrating that the conductance characteristics depend on the length, lateral dimensions, state and degree of disorder, and elongation mechanism of the wire. Conductance during the elongation of short wires (length l approximately 50 angstroms) exhibits periodic quantization steps with characteristic dips, correlating with the order-disorder states of layers of atoms in the wire predicted by molecular dynamics simulations. The resistance R of wires as long as l approximately 400 angstroms exhibits localization characteristics with In R(l) approximately l(2).

Collective and independent-particle motion in two-electron artificial atoms

Investigations of the exactly solvable excitation spectra of two-electron quantum dots with a parabolic confinement, for different values of the parameter R(W) expressing the relative magnitudes of the interelectron repulsion and the zero-point kinetic energy, reveal for large R(W) a rovibrational spectrum associated with a linear trimeric rigid molecule composed of the two electrons and the infinitely heavy confining dot. This spectrum transforms to that of a "floppy" molecule for smaller R(W). The conditional probability distribution calculated for the exact two-electron wave functions allows identification of the rovibrational excitations as rotations and stretching/bending vibrations.

Metal-semiconductor nanocontacts: silicon nanowires

Silicon nanowires assembled from clusters or etched from the bulk, connected to aluminum electrodes and passivated, are studied with large-scale local-density-functional simulations. Short ( approximately 0.6 nm) wires are fully metallized by metal-induced gap states resulting in finite conductance ( approximately e(2)/h). For longer wires ( approximately 2.5 nm) nanoscale Schottky barriers develop with heights larger than the corresponding bulk value by 40% to 90%. Electric transport requires doping dependent gate voltages with the conductance spectra exhibiting interference resonances due to scattering of ballistic channels by the contacts.