Physics

Recent very large molecular dynamics simulations of homogeneous nucleation with (1−8)⋅ 10 9 Lennard-Jones atoms [Diemand et al. J. Chem. Phys. {\bf 139}, 074309 (2013)] allow us to accurately determine the formation free energy of clusters over a wide range of cluster sizes. This is now possible because such large simulations allow for very precise measurements of the cluster size distribution in the steady state nucleation regime. The peaks of the free energy curves give critical cluster sizes, which agree well with independent estimates based on the nucleation theorem. Using these results, we derive an analytical formula and a new scaling relation for nucleation rates: ln J ′ /η is scaled by lnS/η , where the supersaturation ratio is S , η is the dimensionless surface energy, and J ′ is a dimensionless nucleation rate. This relation can be derived using the free energy of cluster formation at equilibrium which corresponds to the surface energy required to form the vapor-liquid interface. At low temperatures (below the triple point), we find that the surface energy divided by that of the classical nucleation theory does not depend on temperature, which leads to the scaling relation and implies a constant, positive Tolman length equal to half of the mean inter-particle separation in the liquid phase.

Bulk gold is a good metal, i.e., conductor of electricity and heat, due to its delocalized electron density that can respond to extremely small external perturbations such as electric field or temperature gradient. In energy space, the quantum states of the conduction electrons cross over the metal's Fermi energy continuously. But when gold is dispersed in finite nanometer-size particles or 'clusters', the delocalized electronic states are re-grouped in energy space to 'shells' according to allowed energy levels and the symmetry and shape of the atomic arrangement. This re-grouping generates also an energy gap in the vicinity of the Fermi energy akin to the energy gap between occupied and unoccupied electron orbitals in molecules. How does the formation of these shells and the energy gap affect the physico-chemical properties of the nanoparticle? How does one get from a 'molecule-like' gold nanoparticle to 'metal-like' gold nanoparticle? Here we analyse the electronic structure and optical and chiroptical properties of recently reported gold nanoparticles of 144, 146, and 246 gold atoms, that are made by wet chemistry methods and whose structures have been resolved to atomic precision. We demonstrate computationally how re-grouping of the quantum states of valence electrons can affect drastically the optical properties of nanoparticles in the crossover-size region, by either generating a multi-band molecule-like or a monotonous metallic optical absorption. The lower the symmetry of the gold core, the more metallic is the nanoparticle. The underlying mechanism arises from symmetry-sensitive distribution of the electronic levels of the nanoparticle close to Fermi energy. Overall, this work sheds lights on fundamental mechanisms on how molecular nanoparticle properties can change metallic in the crossover-size region.

A relation M SHS→LJ between the set of non-isomorphic sticky hard sphere clusters M SHS and the sets of local energy minima M LJ of the (m,n) -Lennard-Jones potential V LJ mn (r)= ε n−m [m r −n −n r −m ] is established. The number of nonisomorphic stable clusters depends strongly and nontrivially on both m and n , and increases exponentially with increasing cluster size N for N≳10 . While the map from M SHS → M SHS→LJ is non-injective and non-surjective, the number of Lennard-Jones structures missing from the map is relatively small for cluster sizes up to N=13 , and most of the missing structures correspond to energetically unfavourable minima even for fairly low (m,n) . Furthermore, even the softest Lennard-Jones potential predicts that the coordination of 13 spheres around a central sphere is problematic (the Gregory-Newton problem). A more realistic extended Lennard-Jones potential chosen from coupled-cluster calculations for a rare gas dimer leads to a substantial increase in the number of nonisomorphic clusters, even though the potential curve is very similar to a (6,12)-Lennard-Jones potential.

We present a combined experimental and theoretical study of the photodissociation of the bisanthenequinone (C28H12O2) cation, Bq+. The experiments show that, upon photolysis, the Bq+ cation does not dehydrogenate, but instead fragments through the sequential loss of the two neutral carbonyl groups, causing the formation of five-membered carbon cycles. Quantum chemical calculations confirm this Bq+ -> [Bq - CO]+ -> [Bq - 2CO]+ sequence as the energetically most favorable reaction pathway. For the first CO loss, a transition state with a barrier of ~3.2 eV is found, substantially lower than the lowest calculated H loss dissociation pathway (~ 4.9 eV). A similar situation applies for the second CO loss channel (~3.8 eV vs. ~4.7 eV), but where the first dissociation step does not strongly alter the planar PAH geometry, the second step transforms the molecule into a bowl-shaped one.

Dipole plasmon resonances are ubiquitous in nano-particles with delocalized charge carriers. Doped semi-conductor colloidal nano-crystals constitute a novel paradigm for plasmon excitations in a finite electron system and offer the possibility to tune the carrier density and thus the dipole resonance from visible to infra-red, which cannot be achieved with metallic clusters. Restricting ourselves to highly n-doped ZnO nano-crystals, we explain the observed smooth transition from small sizes dominated by quantum effects to large sizes where the resonance reaches its classical value. A schematic two interacting highly degenerate level quantum model, validated by a full Random Phase Approximation calculation, yields nicely the experimentally observed trends.

A simple cut-and-patch method is presented for the construction and classification for fullerenes belonging to the octahedral point groups, O or O h . In order to satisfy the symmetry requirement of the octahedral group, suitable numbers of four- and eight-member rings, in addition to the hexagons and pentagons, have to be introduced. An index consisting of four integers is introduced to specify an octahedral fullerenes. However, to specify an octahedral fullerene uniquely, we also found certain symmetry rules for these indices. Based on the transformation properties under the symmetry operations that an octahedral fullerene belongs to, we can identify four structural types of octahedral fullerenes.

Almost ten years ago, energetic neutral hydrogen atoms were detected after a strong-field double ionization of H 2 . This process, called 'frustrated tunneling ionization', occurs when an ionized electron is recaptured after being driven back to its parent ion by the electric field of a femtosecond laser. In the present study we demonstrate that a related process naturally occurs in clusters without the need of an external field: we observe a charge hopping that occurs during a Coulomb explosion of a small helium cluster, which leads to an energetic neutral helium atom. This claim is supported by theoretical evidence. As an analog to 'frustrated tunneling ionization', we term this process 'frustrated Coulomb explosion'.

In this work we define single-particle potentials for a positron and a positronium atom interacting with light atoms (H, He, Li and Be) by inverting a single-particle Schrödinger equation. For this purpose, we use accurate energies and positron densities obtained from the many-body wavefunction of the corresponding positronic systems. The introduced potentials describe the exact correlations for the calculated systems including the formation of a positronium atom. We show that the scattering lengths and the low-energy s-wave phase shifts from accurate many-body calculations are well accounted for by the introduced potential. We also calculate self-consistent two-component density-functional theory positron potentials and densities for the bound positronic systems within the local density approximation. They are in a very good agreement with the many-body results, provided that the finite-positron-density electron-positron correlation potential is used, and they can also describe systems comprising a positronium atom. We argue that the introduced single-particle positron potentials defined for single molecules are transferable to the condensed phase when the inter-molecular interactions are weak. When this condition is fulfilled, the total positron potential can be constructed in a good approximation as the superposition of the molecular potentials.

Photoelectron spectroscopy earlier probed oscillations in C60 valence emissions, producing series of minima whose energy separation depends on the molecular cavity. We show here that the quantum phase at these cavity minima exhibits variations from strong electron correlations in C60, causing rich structures in the emission time delay. Hence, these minima offer unique spectral zones to directly explore multielectron forces via attosecond RABITT interferometry not only in fullerenes, but also in clusters and nanostructures for which such minima are likely abundant.

We provide answers to long-lasting questions in the puzzling behavior of fullerene-fullerene fusion: Why are the fusion barriers so exceptionally high and the fusion cross sections so extremely small? An ab initio nonadiabatic quantum molecular dynamics (NA-QMD) analysis of C 60 +C 60 collisions reveals that the dominant excitation of an exceptionally "giant" oblate-prolate H g (1) mode plays the key role in answering both questions. From these microscopic calculations, a macroscopic collision model is derived, which reproduces the NA-QMD results. Moreover, it predicts analytically fusion barriers for different fullerene-fullerene combinations in excellent agreement with experiments.