The Thermal Stability of Asymmetric Separated Configurations inside Alloy Nanoparticles: Atomic-Scale Modeling of Pd-Ir Nanophase Diagrams.

Compared to alloy bulk phase diagrams, the experimental determination of phase diagrams for alloy nanoparticles (NPs), which are useful in various nanotechnological applications, involves significant technical difficulties, making theoretical modeling a feasible alternative. Yet, being quite challenging, modeling of separation nanophase diagrams is scarce in the literature. The task of predicting comprehensive nanophase diagrams for Pd-Ir face-centered cubic-based three cuboctahedra is facilitated in this study by combining the computationally efficient statistical-mechanical Free-energy Concentration Expansion Method, which includes short-range order (SRO) with coordination-dependent bond-energy variations as part of the input and with rotationally symmetric site grouping for extra efficiency. This nanosystem has been chosen mainly because of the very small atomic mismatch that simplifies the modeling, e.g., in the assessment of vibrational entropy contributions based in this work on fitting to the Pd-Ir experimental bulk critical temperature. This entropic effect, together with SRO, leads to significant destabilization of low-T Quasi-Janus (QJ) asymmetric configurations of the NP core, which transform to symmetric partially mixed nanophases. First-order and second-order intracore transitions are predicted for dilute and intermediate-range compositions, respectively. Caloric curves computed for the former case yield the NP-size dependent transition latent heat, and in the latter case critical temperatures exhibit a specific scaling behavior. The computed separation diagrams and intracore solubility diagrams reflect enhanced elemental mixing in smaller QJ nanophases. In addition to these diagrams, the revealed near-surface compositional variations are likely to be pertinent to the utilization of Pd-Ir NPs, e.g., in catalysis.

Adsorption under nanoconfinement: a theoretical-computational study revealing significant enhancement beyond the Langmuirian levels.

The principal goal of this work is to predict characteristics unique to equilibrated adsorption of a small number of molecules on atomic sites located inside a closed nanoscale space. Compared to the thermodynamic limit of macroscopic systems, significantly enlarged adsorbate coverage under nanoconfinement constitutes a major finding of the modeling. Concomitantly, nanoconfined adsorbates are expected to exhibit extra thermal stability against desorption. These effects on adsorption are explored using canonical partition-functions as well as an original relationship between coverage variations and the Langmuir constant, both in the frameworks of the ideal gas and lattice-gas models. With reported DFT adsorption-energies as input, adsorption isotherms are derived numerically for H2 on Ti-doped graphene-like nanostructures. Remarkable deviations from the classical Langmuir isotherm are predicted for the first time, namely, system-size dependent enhanced H2 adsorbate coverage. The effects are computed also for CO2 inside MOF single-molecule traps, including their relationships to adsorption-energy, specific-heat and to coverage fluctuations. According to preliminary modeling, nanoconfinement effects are anticipated also for adsorption in nanopores undergoing molecular exchange with the external environment, and for impurity segregation in nanoparticle and nanocrystalline solids. The entropic origin of the nanoconfinement effect on equilibrium adsorption (NCEEA) is demonstrated analogously to the nanoconfinement effect on equilibrated chemical reactions studied by us previously. Besides unraveling some basic theoretical issues in physical nanochemistry, this study is expected to be pertinent to nanotechnological applications, such as gas storage and separation in nanoporous materials and other solid adsorbents.

Thermal properties and segregation phenomena in transition metals and alloys: modeling based on modified cohesive-energies.

In spite of free-atom electronic-relaxation contributions to transition-metal cohesive-energies, numerous studies have misused the latter instead of using the solid-state interatomic bond-energy in modeling bulk and surface properties. This work reveals that eliminating the free-atom contributions from experimental cohesive-energies leads to highly accurate linear correlations of the resultant bond-energies with melting temperatures and enthalpies, as well as with inverse thermal-expansion coefficients, specifically for the fcc transition-metals. Likewise, predictions of surface segregation phenomena in Cu-Pd and Au-Pd alloys on the basis of the modified energetics are in much better agreement with reported low-energy ion scattering spectroscopy (LEISS) experimental results, as compared to the use of cohesive-energy values. A last demonstration of the problem and its solution involves the significant impact of the modification on segregation (separation) phase transitions in Cu-Ni model nanoparticles.

Thermally-induced chemical-order transitions in medium-large alloy nanoparticles predicted using a coarse-grained layer model.

A new coarse-grained layer model (CGLM) for efficient computation of axially symmetric elemental equilibrium configurations in alloy nanoparticles (NPs) is introduced and applied to chemical-order transitions in Pt-Ir truncated octahedra (TOs) comprising up to tens of thousands of atoms. The model is based on adaptation of the free energy concentration expansion method (FCEM) using coordination-dependent bond-energy variations (CBEV) as input extracted from DFT-computed elemental bulk and surface energies. Thermally induced quite sharp transitions from low-T asymmetric quasi-Janus and quasi ball-and-cup configurations to symmetric multi-shells furnish unparalleled nanophase composite diagrams for 1289-, 2406- and 4033-atom NPs. At even higher temperatures entropic atomic mixing in the multi-shells gradually intensifies, as reflected in broad heat-capacity Schottky humps, which become sharper for much larger TOs (e.g., ∼10 nm, ∼30,000 atoms), due to transformation to solid-solution-like cores.

Comparative modelling of chemical ordering in palladium-iridium nanoalloys.

Chemical ordering in "magic-number" palladium-iridium nanoalloys has been studied by means of density functional theory (DFT) computations, and compared to those obtained by the Free Energy Concentration Expansion Method (FCEM) using derived coordination dependent bond energy variations (CBEV), and by the Birmingham Cluster Genetic Algorithm using the Gupta potential. Several compositions have been studied for 38- and 79-atom particles as well as the site preference for a single Ir dopant atom in the 201-atom truncated octahedron (TO). The 79- and 38-atom nanoalloy homotops predicted for the TO by the FCEM/CBEV are shown to be, respectively, the global minima and competitive low energy minima. Significant reordering of minima predicted by the Gupta potential is seen after reoptimisation at the DFT level.

Stabilization and transformation of asymmetric configurations in small-mismatch alloy nanoparticles: the role of coordination dependent energetics.

Chemical order in platinum-iridium truncated-octahedron nanoparticles as a model system was studied using coordination-dependent bond-energy variations (CBEV) and the statistical-mechanical free-energy concentration expansion method (FCEM) adapted for handling axially symmetric structures. Pt-Ir side-separated ("Quasi-Janus", QJ) configurations are found to be stabilized at low temperatures mainly due to CBEV-related preferential strengthening of Pt-surface-Ir-subsurface bonds, and the greatly reduced number of hetero-atomic bonds. In comparison, the roles of local strain (by only ~2% atomic mismatch), short-range-order and vibrational entropy are minor. At higher temperatures, the QJ configuration is transformed into a partially disordered central-symmetric onion-like structure, and the sharp transition is accompanied by extensive pre-transition atomic exchange processes, reflected in a lambda-type heat capacity curve. The nanoparticle composition and size dependent transition temperatures, which are well below the bulk miscibility gap, furnish the first Pt-Ir nanophase diagram, which is likely to represent a distinct class of asymmetrically phase-separated nanoalloys having negligible mismatch but large preferential bond strengthening at the near-surface region.

The intrinsic role of nanoconfinement in chemical equilibrium: evidence from DNA hybridization.

Recently we predicted that when a reaction involving a small number of molecules occurs in a nanometric-scale domain entirely segregated from the surrounding media, the nanoconfinement can shift the position of equilibrium toward products via reactant-product reduced mixing. In this Letter, we demonstrate how most-recently reported single-molecule fluorescence measurements of partial hybridization of ssDNA confined within nanofabricated chambers provide the first experimental confirmation of this entropic nanoconfinement effect. Thus, focusing separately on each occupancy-specific equilibrium constant, quantitatively reveals extra stabilization of the product upon decreasing the chamber occupancy or size. Namely, the DNA hybridization under nanoconfined conditions is significantly favored over the identical reaction occurring in bulk media with the same reactant concentrations. This effect, now directly verified for DNA, can be relevant to actual biological processes, as well as to diverse reactions occurring within molecular capsules, nanotubes, and other functional nanospaces.

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

Patchy multishell segregation in Pd-Pt alloy nanoparticles.

Chemical ordering in face-centered-cubic-like PdPt nanoparticles consisting of 38-201 atoms is studied via density-functional calculations combined with a symmetry orbit approach. It is found that for larger particles in the Pd-rich regime, Pt atoms can segregate at the center of the nanoparticle (111) surface facets, in contrast with extended systems in which Pd is known to segregate at the surface of alloy planar surfaces. In a range of compositions around 1:1, a novel multishell chemical ordering pattern was favored, in which each shell is a patchwork of islands of atoms of the two elements, but the order of the patchwork is reversed in the alternating shells. These findings are rationalized in terms of coordination-dependent bond-energy variations in the metal-metal interactions, and their implications in terms of properties and applications of nanoscale alloy particles are discussed.

Nanochemical equilibrium involving a small number of molecules: a prediction of a distinct confinement effect.

The equilibrium state of a reaction mixture comprised of a small number of molecules is modeled for three different nanoconfined systems. The issue is relevant to several advanced routes for the synthesis of encapsulated organic molecules, metallic or inorganic nanoclusters, and other nanoscale structures. Canonical-ensemble based formulations and computations predict for the equilibrated closed small systems significant deviations from the (macroscopic) thermodynamic limit. The effects include the enhancement/suppression of the equilibrium extent of the exothermic/endothermic model reactions, associated mainly with reduced numbers of mixed reactant-product microstates in the closed system. Fluctuations in the nanochemical reaction extent, which are found to be closely related to the stoichiometric coefficients, become more dominant for smaller systems and modify considerably the temperature dependence of the equilibrium constant.