Quantum decoherence in finite size exciton-phonon systems

Based on the operatorial formulation of the perturbation theory, the properties of a confined exciton coupled with phonons in thermal equilibrium is revisited. Within this method, the dynamics is governed by an effective Hamiltonian which accounts for exciton-phonon entanglement. The exciton is dressed by a virtual phonon cloud whereas the phonons are clothed by virtual excitonic transitions. Special attention is thus paid for describing the time evolution of the excitonic coherences at finite temperature. As in an infinite lattice, temperature-enhanced quantum decoherence takes place. However, it is shown that the confinement softens the decoherence. The coherences are very sensitive to the excitonic states so that the closer to the band center the state is located, the slower the coherence decays. In particular, for odd lattice sizes, the coherence between the vacuum state and the one-exciton state exactly located at the band center survives over an extremely long time scale. A superimposition involving the vacuum and this specific one-exciton state behaves as an ideal qubit insensitive to its environment.     

Orbital magnetization in extended systems.

While the orbital magnetic dipole moment of any finite sample is well-defined, it becomes ill-defined in the thermodynamic limit as a result of the unboundedness of the position operator. Effects due to surface currents and to bulk magnetization are not easily disentangled. The corresponding electrical problem, where surface charges and bulk polarization appear as entangled, was solved about a decade ago by the modern theory of polarization, based on a Berry phase. We follow a similar path here, making progress toward a bulk expression for the orbital magnetization in an insulator represented by a lattice-periodic Hamiltonian with broken time-reversal symmetry. We therefore limit ourselves to the case where the macroscopic (i.e. cell-averaged) magnetic field vanishes. We derive an expression for the contribution to the magnetization arising from the circulating currents internal to the bulk Wannier functions, and then transform to obtain a Brillouin zone integral involving the occupied Bloch orbitals. A version suitable for practical implementation in discretized reciprocal space is also derived, and the gauge invariance of both versions is explicitly shown. However, tests on a tight-binding model indicate the presence of additional edge currents, and it remains to be determined whether these can be related to the bulk band structure.     

Elastic models,lattice dynamics and finite size effects in molecular spin crossover systems

The experimental studies of spin-crossover compounds switched in the last decade from bulk measurements and macroscopic observations to the nanoscale and microscopic approaches. In this context, new and sometimes unexpected behaviours have been documented, which could be partially described only by the classical phenomenological models developed in the last period of the last century. In this context, the development of more complex models, able to reproduce the nucleation and domain propagation within the material, has proved to be not a whim of some theoreticians but a necessity, which facilitated the full understanding of observed phenomena and even made premises for further experiments. Here, we present and analyse various elastic models identifying their common points and differences and discuss how they can be used for the study of microscopic phenomena as the cluster formation, stability and propagation or for the study of finite size effects in spin-crossover nanoparticles, with open boundary conditions or embedded in various matrices.     

Orbital decimation in molecular systems with an AM1 Hamiltonian

Green's function method, with a renormalization strategy that allows for stepwise hierarchical decimation of orbitals. is a powerful technique for calculations in very large molecular systems. An interesting aspect of the decimation method is its relationship with the concepts of supramolecular chemistry. For donor-acceptor bridged systems, for example, decimation may be done to find a two level representation, with an effective through-bond interaction, that is considered to control long distance electron-transfer in biological and other supramolecular systems. In the present work the decimation was applied for molecular systems with an AM 1 Hamiltonian, that allows for geometry optimization and self-consistence.     

Vibron-polaron critical localization in a finite size molecular nanowire

The small polaron theory is applied to describe the vibron dynamics in an adsorbed nanowire with a special emphasis onto finite size effects. It is shown that the finite size of the nanowire discriminates between side molecules and core molecules which experience a different dressing mechanism. Moreover, the inhomogeneous behavior of the polaron hopping constant is established and it is shown that the core hopping constant depends on the lattice size. However, the property of a lattice with translational invariance is recovered when the size of the nanowire is greater than a critical value. Finally, it is pointed out that these features yield the occurrence of high energy localized states in which both the nature and the number are summarized in a phase diagram in terms of the relevant parameters of the problem (small polaron binding energy, temperature, lattice size).     

Hydrodynamic fractionation of finite size gold nanoparticle clusters

We demonstrate a high-resolution in situ experimental method for performing simultaneous size classification and characterization of functional gold nanoparticle clusters (GNCs) based on asymmetric-flow field flow fractionation (AFFF). Field emission scanning electron microscopy, atomic force microscopy, multi-angle light scattering (MALS), and in situ ultraviolet-visible optical spectroscopy provide complementary data and imagery confirming the cluster state (e.g., dimer, trimer, tetramer), packing structure, and purity of fractionated populations. An orthogonal analysis of GNC size distributions is obtained using electrospray-differential mobility analysis (ES-DMA). We find a linear correlation between the normalized MALS intensity (measured during AFFF elution) and the corresponding number concentration (measured by ES-DMA), establishing the capacity for AFFF to quantify the absolute number concentration of GNCs. The results and corresponding methodology summarized here provide the proof of concept for general applications involving the formation, isolation, and in situ analysis of both functional and adventitious nanoparticle clusters of finite size.     

Drop size prediction in liquid membrane systems

The design of separation equipment using liquid membranes requires predictive methods for the estimation of drop diameters of the dispersed liquid membrane “macrodrop”. Existing models for drop breakage in liquid-liquid systems underpredict drop diameters of liquid membrane macrodrops even after incorporating the effects of dispersed phase viscosity and hold-up. By considering that the microdroplets within a liquid membrane macrodrop cause a damping of induced drop oscillations arising from external turbulence, the recently proposed model of Calabrese et al. (1986) has been modified and the resulting model equations have been shown to predict drop diameters of both oil as well as water liquid membrane macrodrops reasonably well.     

Interplay among aromaticity, magnetism, and nonlinear optical response in all-metal aromatic systems

All-metal aromatic molecules are the latest inclusion in the family of aromatic systems. Two different classes of all-metal aromatic clusters are primarily identified: one is aromatic only in the low spin state, and the other shows aromaticity even in high-spin situations. This observation prompts us to investigate the effect of spin multiplicity on aromaticity, taking Al(4)(2-), Te(2)As(2)(2-), and their copper complexes as reference systems. Among these clusters, it has been found that the molecules that are aromatic only in their singlet state manifest antiaromaticity in their triplet state. The aromaticity in the singlet state is characterized by the diatropic ring current circulated through the bonds, which are cleaved to generate excess spin density on the atoms in the antiaromatic triplet state. Hence, in such systems, an antagonistic relationship between aromaticity and high-spin situations emerges. On the other hand, in the case of triplet aromatic molecules, the magnetic orbitals and the orbitals maintaining aromaticity are different; hence, aromaticity is not depleted in the high-spin state. The nonlinear optical (NLO) behavior of the same set of clusters in different spin states has also been addressed. We correlate the second hyperpolarizability and spin density in order to judge the effect of spin multiplicity on third-order NLO response. This correlation reveals a high degree of NLO behavior in systems with excess spin density. The variance of aromaticity and NLO response with spin multiplicity is found to stem from a single aspect, the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and eventually the interplay among aromaticity, magnetism, and NLO response in such materials is established. Hence, the HOMO-LUMO energy gap becomes the cornerstone for tuning the interplay. This correlation among the said properties is not system-specific and thus can be envisaged even beyond the periphery of all-metal aromatic clusters. Such interplay is of crucial importance in tailoring novel paradigm of multifunctional materials.     

Orbital interactions in large molecular systems: Adsorption of H2 on Ni surfaces

The concept of orbital interactions is applied to the adsorption of H₂ on to the Ni (110) and (111) surfaces. We calculate first two orbitals of a Ni cluster one of which forms an orbital pair with the σ MO and the other with the σ*MO of a H₂ molecule. Contributions of these paired orbitals of fragments to the density of states of the surface-adsorbate extended system are then examined. It is shown that the orbital of the surface that participates in electron delocalization to σ* of the H₂ molecule is located significantly below the Fermi level both in the (110) and in the (111) adsorption models. The σ MO of H₂ and its counterpart of the surface represent mainly overlap repulsion which is shown to be stronger on the (111) surface than on the (110) surface. It is feasible to understand chemical interactions of large systems by using the paired interacting orbitals.     

Effects of finite size nuclei in relativistic four-component calculations of hyperfine structure

The effect of a finite size model for both the nuclear charge and magnetic moment distributions on calculated EPR hyperfine structure have been studied using a relativistic four-component method based on density functional theory. This approach employs a restricted kinetically balanced basis (mDKS-RKB) and includes spin-polarization using noncollinear spin-density exchange-correlation functionals in the unrestricted fashion. Benchmark calculations have been carried out for a number of small molecules containing Zn, Cd, Ag, and Hg. The present results are compared with those obtained at the Douglas-Kroll-Hess second order (DKH-2) method. The dependence of the results on the quality of the orbital and auxiliary basis sets has been studied. It was found that some basis sets contain irregularities that deteriorate the results. Especial care has to be taken also on the construction of the auxiliary basis for fitting the total electron and spin-densities.     

Cluster magnetism in doped InSb

Magnetic properties of indium antimonide doped by Mn and by, simultaneously, Mn and Zn, and Mn and Cd have been analyzed. It has been established that the basic contribution to the formation of the magnetic properties of these materials comes from clusters, whose composition and Curie temperature change depending on the content of manganese, zinc, and cadmium.     

Penetration and displacement in capillary systems of limited size

The unique features of capillary penetration and displacement in systems of limited size are described. These include the dependence of the criteria and kinetics of penetration and displacement on the curvatures of the liquid reservoirs, the effect of thinness of the porous medium on the extent of penetration (the reexposure effect); and the effect of nonuniformity in the pore size distribution on the kinetics of penetration (the redistribution effect). It is shown that systems of limited size may be characterized by thermodynamic equilibrium states as well as kinetics, which are very different from those associated with large systems.     

Single-molecule magnetism in cyclopentadienyl-dysprosium chlorides

[Cp(2)Dy(thf)(μ-Cl)](2) (2) was synthesized from [Cp(2)Dy(μ-Cl)](n), which crystalizes as two polymorphs, with n = 2 (1a) or ∞ (1b). All three compounds show slow relaxation of magnetization, and in 2 the quantum tunnelling was found to be exchange-biased.     

Nanochemistry and magnetism

An analysis of magnetism of nanochemical systems opens up new ways to creating ferromagnets from diamagnetic substances and new principles for constructing molecular ferromagnets, hybrid magnetic materials, and monomolecular magnets on the basis of high-spin molecules and complexes. Their use in spin computing is considered.     

Dynamical motions of lipids and a finite size effect in simulations of bilayers

Molecular dynamics (MD) simulations of dipalmitoylphosphatidylcholine bilayers composed of 72 and 288 lipids are used to examine system size dependence on dynamical properties associated with the particle mesh Ewald (PME) treatment of electrostatic interactions. The lateral diffusion constant Dl is 2.92 x 10(-7) and 0.95 x 10(-7) cm2/s for 72 and 288 lipids, respectively. This dramatic finite size effect originates from the correlation length of lipid diffusion, which extends to next-nearest neighbors in the 288 lipid system. Consequently, diffusional events in smaller systems can propagate across the boundaries of the periodic box. The internal dynamics of lipids calculated from the PME simulations are independent of the system size. Specifically, reorientational correlation functions for the slowly relaxing phosphorus-glycerol hydrogen, phosphorus-nitrogen vectors, and more rapidly relaxing CH vectors in the aliphatic chains are equivalent for the 72 and 288 lipid simulations. A third MD simulation of a bilayer with 72 lipids using spherical force-shift electrostatic cutoffs resulted in interdigitated chains, thereby rendering this cutoff method inappropriate.     

Effect of finite size on cooperativity and rates of protein folding

We analyze the dependence of cooperativity of the thermal denaturation transition and folding rates of globular proteins on the number of amino acid residues, N, using lattice models with side chains, off-lattice Go models, and the available experimental data. A dimensionless measure of cooperativity, Omega(c) (0 < Omega(c) < infinity), scales as Omega(c) approximately N(zeta). The results of simulations and the analysis of experimental data further confirm the earlier prediction that zeta is universal with zeta = 1 + gamma, where exponent gamma characterizes the susceptibility of a self-avoiding walk. This finding suggests that the structural characteristics in the denaturated state are manifested in the folding cooperativity at the transition temperature. The folding rates k(F) for the Go models and a dataset of 69 proteins can be fit using k(F) = k(F)0 exp(-cN(beta)). Both beta = 1/2 and 2/3 provide a good fit of the data. We find that k(F) = k(F)0 exp(-cN(1/2)), with the average (over the dataset of proteins) k(F)0 approximately (0.2 micros)(-1) and c approximately 1.1, can be used to estimate folding rates to within an order of magnitude in most cases. The minimal models give identical N dependence with c approximately 1. The prefactor for off-lattice Go models is nearly 4 orders of magnitude larger than the experimental value.     

Doping induced magnetism in Co-ZnS nanoparticles

Zn_1−xCo_xS nanoparticles with x=0, 0.1, 0.2, and 0.3 were synthesized by the co-precipitation method using thiophenol as capping agent. The effect of Co doping on the structural, optical and magnetic properties are investigated. The X-ray diffraction patterns show single phase with cubic structure and the images of Transmission Electron Microscopy indicate an average particle size of 39 nm. Significant blue shift in the optical absorbing band edge was observed with increasing Co doping. In the Co doped samples, room-temperature (RT) magnetic hysteresis is observed and the magnetization reduces with increasing Co content. However, these samples show paramagnetic resonance instead of ferromagnetic resonance at both 300 and 80 K, suggesting that the origin of RT magnetization in these Zn_1−xCo_xS nanoparticles involves with the frustration of antiferromagnetic interactions.     

Softening the long-wavelength electromagnetic response of finite quantal systems

The long wavelength electromagnetic response of finite quantal systems depend on the spill-out of fermions from the surface of the system as well as on its deformation, as testified by the analysis of results obtained for fullerenes C₆₀, C₇₀, C₉₀, C₁₁₀ and C₂₈H_n, as well as for alkali metal clusters, in particular Na₈. Similar results are also found in the study of the electromagnetic response of atomic nuclei.