High pressure studies on nanometer sized clusters: Structural, optical, and cooperative properties

High-pressure Se EXAFS is used to study pressure-induced structural transformations in CdSe nanocrystals. The transformation is wurtzite to rock salt, at a pressure much higher than in bulk. High-pressure XRD is used to confirm the EXAFS results. Diffraction peak widths indicate that nanocrystals do not fragment upon transformation. Optical absorption correlates with structural transformations and is used to measure transition pressures; transformation pressure increases smoothly as nanocrystal size decreases. Thermodynamics of transformation is modeled using an elevated surface energy in the high-pressure phase. High-pressure study of Si nanocrystals show large increases in transformation pressure in crystallites to 500{angstrom} diameter, and an overall change in crystallite shape upon transformation is seen from XRD line widths. C{sub 60} single crystals were studied using Raman scattering; results provide information about the clusters` rotational state. Optical properties of high-pressure phase CdSe clusters were studied

HighP–TNano-Mechanics of Polycrystalline Nickel

We have conducted highP–Tsynchrotron X-ray and time-of-flight neutron diffraction experiments as well as indentation measurements to study equation of state, constitutive properties, and hardness of nanocrystalline and bulk nickel. Our lattice volume–pressure data present a clear evidence of elastic softening in nanocrystalline Ni as compared with the bulk nickel. We show that the enhanced overall compressibility of nanocrystalline Ni is a consequence of the higher compressibility of the surface shell of Ni nanocrystals, which supports the results of molecular dynamics simulation and a generalized model of a nanocrystal with expanded surface layer. The analytical methods we developed based on the peak-profile of diffraction data allow us to identify “micro/local” yield due to high stress concentration at the grain-to-grain contacts and “macro/bulk” yield due to deviatoric stress over the entire sample. The graphic approach of our strain/stress analyses can also reveal the corresponding yield strength, grain crushing/growth, work hardening/softening, and thermal relaxation under highP–Tconditions, as well as the intrinsic residual/surface strains in the polycrystalline bulks. From micro-indentation measurements, we found that a low-temperature annealing (T < 0.4 Tm) hardens nanocrystalline Ni, leading to an inverse Hall–Petch relationship. We explain this abnormal Hall–Petch effect in terms of impurity segregation to the grain boundaries of the nanocrystalline Ni

High pressure studies on nanometer sized clusters: Structural, optical, and cooperative properties

High-pressure Se EXAFS is used to study pressure-induced structural transformations in CdSe nanocrystals. The transformation is wurtzite to rock salt, at a pressure much higher than in bulk. High-pressure XRD is used to confirm the EXAFS results. Diffraction peak widths indicate that nanocrystals do not fragment upon transformation. Optical absorption correlates with structural transformations and is used to measure transition pressures; transformation pressure increases smoothly as nanocrystal size decreases. Thermodynamics of transformation is modeled using an elevated surface energy in the high-pressure phase. High-pressure study of Si nanocrystals show large increases in transformation pressure in crystallites to 500{angstrom} diameter, and an overall change in crystallite shape upon transformation is seen from XRD line widths. C{sub 60} single crystals were studied using Raman scattering; results provide information about the clusters` rotational state. Optical properties of high-pressure phase CdSe clusters were studied

Atomistic simulations of pressure-induced structural transformations in solids

Constant-pressure MD simulations complement constant-volume MD simulations and naturally allow the study of systems where external pressure is a driving force for a structural transformation. These transformations take place in crystalline as well as amorphous systems. Besides studies of bulk systems there is also growing interest in simulations of finite systems, such as clusters and nanocrystals, under pressure. In the paper we review various approaches to constant pressure simulations with focus on the recent developments in simulation methodology, such as metadynamics and transition path sampling. The application of the techniques to bulk and finite systems is illustrated on several examples