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Vitaly V. Kresin

Publications and source records attributed to Vitaly V. Kresin.

36 records · Page 2Linked to original sources
arXiv2015

Proton transfer in histidine-tryptophan heterodimers embedded in helium droplets

We used cold helium droplets as nano-scale reactors to form and ionize, by electron bombardment and charge transfer, aromatic amino acid heterodimers of histidine with tryptophan, methyl-tryptophan, and indole. The molecular interaction occurring through an N-H...N hydrogen bond leads to a proton transfer from the indole group of tryptophan to the imidazole group of histidine in a radical cationic environment.

physics.atm-clus↗
arXiv2015

Electric dipole moments of nanosolvated acid molecules in water clusters

The electric dipole moments of $(H_{2}O)_{n}DCl$ ($n=3-9$) clusters have been measured by the beam deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at $n\approx5-6$. This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters, and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.

physics.atm-clus↗
arXiv2014

A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T>~100K

A unique property of size-resolved metal nanocluster particles is their "superatom"-like electronic shell structure. The shell levels are highly degenerate, and it has been predicted that this can enable exceptionally strong superconducting-type electron pair correlations in certain clusters composed of just tens to hundreds of atoms. Here we report on the observation of a possible spectroscopic signature of such an effect. A bulge-like feature appears in the photoionization yield curve of a free cold aluminum cluster and shows a rapid rise as the temperature approaches approximately 100 K. This is an unusual effect, not previously reported for clusters. Its characteristics are consistent with an increase in the effective density of states accompanying a pairing transition, which suggests a high-temperature superconducting state with Tc>~100 K. Our results highlight the promise of metal nanoclusters as high-Tc building blocks for materials and networks.

cond-mat.supr-con↗
arXiv2014

Flat Thomas-Fermi artificial atoms

We consider two-dimensional (2D) "artificial atoms" confined by an axially symmetric potential $V(ρ)$. Such configurations arise in circular quantum dots and other systems effectively restricted to a 2D layer. Using the semiclassical method, we present the first fully self-consistent and analytic solution yielding equations describing the density distribution, energy, and other quantities for any form of $V(ρ)$ and an arbitrary number of confined particles. An essential and nontrivial aspect of the problem is that the 2D density of states must be properly combined with 3D electrostatics. The solution turns out to have a universal form, with scaling parameters $ρ^2/R^2$ and $R/a_B^*$ ($R$ is the dot radius and $a_B^*$ is the effective Bohr radius).

cond-mat.mes-hall↗
arXiv2012

Photoionization profiles of metal clusters and the Fowler formula

Metal cluster ionization potentials are important characteristics of these "artificial atoms," but extracting these quantities from cluster photoabsorption spectra, especially in the presence of thermal smearing, remains a big challenge. Here we demonstrate that the classic Fowler theory of surface photoemission does an excellent job of fitting the photoabsorption profile shapes of neutral In_{n=3-34} clusters [Wucher et al., New J. Phys. 10, 103007 (2008)]. The deduced ionization potentials extrapolate precisely to the bulk work function, and the internal cluster temperatures are in close agreement with values expected for an ensemble of freely evaporating clusters. Supplementing an earlier application to potassium clusters, these results suggest that the Fowler formalism, which is straightforward and physical, may be of significant utility in metal cluster spectroscopy. It is hoped also that the results will encourage a comprehensive theoretical analysis of the applicability of bulk-derived models to cluster photoionization behavior, and of the transition from atomic and molecular-type to surface-type photoemission.

physics.atm-clus↗
arXiv2011

Beam broadening of polar molecules and clusters in deflection experiments

A beam of rotating dipolar particles (molecules or clusters) will broaden when passed through an electric or magnetic field gradient region. This broadening, which is a common experimental observable, can be expressed in terms of the variance of the distribution of the resulting polarization orientation (the direction cosine). Here the broadening for symmetric-top and linear rotors is discussed. These two types of rotors have qualitatively different low-field orientation distribution functions, but behave similarly in a strong field. While analytical expressions for the polarization variance can be derived from first-order perturbation theory, for experimental guidance it is important to identify the applicability and limitations of these expressions, and the general dependence of the broadening on the experimental parameters. For this purpose, the analytical results are compared with the full diagonalization of the rotational Stark-effect matrices. Conveniently for experimental estimations, it is found that for symmetric tops the dependence of the broadening parameter on the rotational constant, the axial ratio, and the field strength remains similar to the analytical expression even outside of the perturbative regime. Also, it is observed that the shape envelope, the centroid, and the width of the orientation distribution function for a symmetric top are quite insensitive to the value of its rotational constant (except at low rotational temperatures).

physics.atm-clus↗
arXiv2011

Slow electron attachment as a probe of cluster evaporation processes

Neutral alkali clusters efficiently capture low-energy electrons with the aid of long-range polarization attraction. Upon attachment, the electron affinity and kinetic energy are dissipated into vibrations, heating the cluster and triggering evaporation of atoms and dimers. This process offers a novel means to explore nanocluster bonding and evaporation kinetics. The present work investigates the formation of ${Na}_N^-$. A crossed-beam experiment reveals that relative anion abundances become strongly and nontrivially restructured with respect to the neutral precursor beam. This restructuring is explained in quantitative detail by an analysis of evaporative cascades initiated by the attachment. The analysis thus furnishes a complete description of the electron attachment process, from initial attraction to final rearrangement of the cluster population. In addition, the paper describes a systematic derivation of cluster evaporation kinetics and internal temperature distributions; a new relation between the dissociation energies of cationic, neutral and anionic metal clusters; and a scenario for inferring the neutral cluster population in the supersonic beam from the cationic mass spectrum.

physics.atm-clus↗
arXiv2009

Minimum sizes for the submersion of alkali clusters into liquid helium

Alkali atoms do not stably embed in liquid helium-4 because the interatomic attractive potential is unable to overcome the short-range Pauli repulsion of the s electrons and the surface tension cost of the surrounding bubble. Similarly, small alkali complexes reside on the surface of helium nanodroplets instead of inside. However, as the size of the metal cluster increases, its van der Waals attraction to the helium matrix grows faster than the repulsive energies and above a certain size it should become favorable for clusters to submerge in the liquid. Based on an evaluation of the relevant energy terms, we characterize the bubble dimensions and estimate the critical submersion sizes. The latter range from N~20 for Li_N and Na_N to N>100 for Rb_N in helium-4 and from N~5 for Li_N and Na_N to N~20 for Cs_N in helium-3. These results are discussed in the context of nanodroplet pick-up experiments with alkali atoms

physics.atm-clus↗
arXiv2009

Electric dipole moments of nitric acid-water complexes measured by cluster beam deflection

Water clusters embedding a nitric acid molecule HNO3(H2O)_{n=1-10} are investigated via electrostatic deflection of a molecular beam. We observe large paraelectric susceptibilities that greatly exceed the electronic polarizability, revealing the contribution of permanent dipole moments. The moments derived from the data are also significantly higher than those of pure water clusters. An enhancement in the susceptibility for n=5,6 and a rise in cluster abundances setting in at n=6 suggest that dissociation of the solvated acid molecule into ions takes place in this size range.

physics.atm-clus↗
arXiv2009

Photoabsorption by Volume Plasmons in Metal Nanoclusters

It is well known that plasmons in bulk metals cannot be excited by direct photoabsorption, that is, by coupling of volume plasmons to light. Here we demonstrate that the situation in nanoclusters of the same metals is entirely different. We have carried out a photodepletion measurement for Na_20 and Na_92 and identified a broad volume plasmon absorption peak centered slightly above 4 eV, revealing the possibility of optical excitation of volume-type collective electronic modes in a metallic system. The observed phenomenon is related to different selection rules for finite systems.

physics.atm-clus↗
arXiv2008

Evaporative attachment of slow electrons to alkali nanoclusters

The abundance spectrum of Na^-_{n~7-140} anions formed by low energy electron attachment to free nanoclusters is measured to be strongly and nontrivially restructured with respect to the neutral precursor beam. This restructuring is explained in quantitative detail by a general framework of evaporative attachment: an electron is captured by the long-range polarization potential, its energy is transferred into thermal vibrations, and dissipated by evaporative cooling. The data also affirm a formulated relation between the binding energies of cationic, neutral, and anionic clusters, and an adjustment to the prior values of dimer evaporation energies.

physics.atm-clus↗
arXiv2007

Suppressing the fragmentation of fragile molecules in helium nanodroplets by co-embedding with water: Possible role of the electric dipole moment

When fragile molecules such as glycine, polyglicine, alkanes, and alkanethiols are embedded in liquid helium nanodroplets, electron-impact ionization of the beam leads to fragmentation which is as extensive as that of isolated gas-phase molecules. However, it turns out that if a few molecules of water are co-embedded with the peptide and alkane chains, their fragmentation is drastically reduced or completely eliminated. On the other hand, the fragmentation of alkanethiols remains unaffected. On the basis of these observations, it is proposed that the fragmentation "buffering" effect may correlate with the magnitude of the impurity's electric dipole moment, which steers the migration of the ionizing He^+ hole in the droplet.

physics.atm-clus↗
arXiv2007

Density of states of helium droplets

Accurate analytical expressions for the state densities of liquid He-4 droplets are derived, incorporating the ripplon and phonon degrees of freedom. The microcanonical temperature and the ripplon angular momentum level density are also evaluated. The approach is based on inversions and systematic expansions of canonical thermodynamic properties.

physics.atm-clus↗
arXiv2007

Surface location of alkaline-earth atom impurities on helium nanodroplets

There has been notable uncertainty regarding the degree of solvation of alkaline-earth atoms, especially Mg, in free He-4 nanodroplets. We have measured the electron energy dependence of the ionization yield of picked-up atoms. There is a qualitative shape difference between the yield curves of species solvated in the middle of the droplet and species located in the surface region; this difference arises from the enhanced role played by the Penning ionization process in the latter case. The measurements demonstrate that Mg, Ca, Sr and Ba all reside at or near the droplet surface.

cond-mat.other↗
arXiv2006

Electrostatic deflection of the water molecule, a fundamental asymmetric rotor

An inhomogeneous electric field is used to study the deflection of a supersonic beam of water molecules. The deflection profiles show strong broadening accompanied by a small net displacement towards higher electric fields. The profiles are in excellent agreement with a calculation of rotational Stark shifts. The molecular rotational temperature being the only adjustable parameter, beam deflection is found to offer an accurate and practical means of determining this quantity. A pair of especially strongly responding rotational sublevels, adding up to \approx 25% of the total beam intensity, are readily separated by deflection, making them potentially useful for further electrostatic manipulation.

physics.chem-ph↗
arXiv2005

Fast electronic relaxation in metal nanoclusters via excitation of coherent shape deformations: Circumventing a bottleneck

Electron-phonon relaxation in size-quantized systems may become inhibited when the spacing of discrete electron energy levels exceeds the magnitude of the phonon frequency. We show, however, that nanoclusters can support a fast nonradiative relaxation channel which derives from their distinctive ability to undergo Jahn-Teller shape deformations. Such a deformation represents a collective and coherent vibrational excitation and enables electronic transitions to occur without a multiphonon bottleneck. We analyze this mechanism for a metal cluster within the analytical framework of a three-dimensional potential well undergoing a spheroidal distortion. An expression for the time evolution of the distortion parameter is derived, the electronic level crossing condition formulated, and the probability of electronic transition at a level crossing is evaluated. An application to electron-hole recombination in a closed-shell aluminum cluster with 40 electrons shows that the short (~250 fs) excitation lifetime observed in recent pump-probe experiments can be explained by the proposed mechanism.

physics.atm-clus↗
arXiv2002

Work functions, ionization potentials, and in-between: Scaling relations based on the image charge model

We revisit a model in which the ionization energy of a metal particle is associated with the work done by the image charge force in moving the electron from infinity to a small cut-off distance just outside the surface. We show that this model can be compactly, and productively, employed to study the size dependence of electron removal energies over the range encompassing bulk surfaces, finite clusters, and individual atoms. It accounts in a straightforward manner for the empirically known correlation between the atomic ionization potential (IP) and the metal work function (WF), IP/WF$\sim$2. We formulate simple expressions for the model parameters, requiring only a single property (the atomic polarizability or the nearest neighbor distance) as input. Without any additional adjustable parameters, the model yields both the IP and the WF within $\sim$10% for all metallic elements, as well as matches the size evolution of the ionization potentials of finite metal clusters for a large fraction of the experimental data. The parametrization takes advantage of a remarkably constant numerical correlation between the nearest-neighbor distance in a crystal, the cube root of the atomic polarizability, and the image force cutoff length. The paper also includes an analytical derivation of the relation of the outer radius of a cluster of close-packed spheres to its geometric structure.

physics.atm-clus↗