Physics

Photoionization studies of Na20 and Na92 clusters are carried out in a framework of linear response density functional theory. Cross sections show substantial spillover of plasmon resonances to the near-threshold ionization energies which are in reasonable agreements with measurements. The analysis of the oscillator strength, consumed by the cross section, lends further insights. The many-body interaction induced self-consistent field from density fluctuations suggests the existence of an attractive force. This may cause time-delayed plasmonic photoemissions in ultrafast measurements. At the waning end of the plasmon structure, a strong minimum in the cross sections from a correlation-driven coherence effect is predicted which can possibly be observed by the photoelectron spectroscopy.

There is considerable interest in collective effects in hybrid systems formed by molecular or atomic ensembles strongly coupled by an electromagnetic resonance. For analyzing such collective effects, we develop an efficient and general theoretical formalism based on the natural modes of the resonator. The main strength of our approach is its generality and the high level of analyticity enabled by modal analysis, which allows one to model complex hybrid systems without any restriction on the resonator shapes or material properties, and to perform statistical computations to predict general properties that are robust to spatial and polarization disorders. Most notably, we establish that superradiant modes remain even after ensemble averaging and act as an invisibility cloak with a spectral bandwidth that scales with the number of oscillators and the spatially-averaged Purcell factor.

Gas-phase oxygen-rich iron oxide clusters Fe(O2)n+ (n=1-6), are produced in a molecular beam apparatus. Their stability and structure are investigated by measuring the fragmentation cross sections from collision-induced-dissociation experiments. For this purpose, two different techniques have been employed. The first one relies on the measurement of the fragments resulting after collisional activation and subsequent dissociation of mass selected cluster ions in a molecular beam passing through a cell filled with noble gas atoms. The second one is a new approach that we introduce and is based on crossed molecular beams to measure the fragmentation cross sections, in a more efficient manner without mass selection of the individual clusters. The cross sections obtained with the different techniques are compared with each other as well as with theoretical ones resulting from the application of a simple geometrical projection model. Finally, the general trends observed are compared with results for other Fe-molecule clusters available in the literature.

The comment by K. Hansen suggests that the time-of-flight mass spectrometry data in one table in our paper from 2103 in IJMS should be due to a proton contamination and correspond to protons p instead of deuterons D. The evidence for such a suggestion is a re-plotting of our data, giving a bond distance of 5.0 pm instead of 2.3 pm, corresponding to state s = 3 instead of s = 2 in the ultra-dense hydrogen. However, protium has indeed been studied on the next pages in our paper, giving shorter time-of-flights as expected. A replotting of our protium results as suggested by Hansen gives a best fit mass of 0.6 u, showing that the suggested procedure gives consistently too small mass. Hansen also rejects the rotational energy transfer model as due to our use of D in the analysis of the data. However, this model has been applied successfully in two previous publications, including experiments using protium. Hansen also suggests that the protium is due to a contamination of the source; however, the gas feed (H2 or D2) and its result is well controlled and monitored. The most likely source of protons was instead laser-induced nuclear fusion, but the laser intensity in these experiments was a factor three too low to give strong fusion. Thus, the suggestion by Hansen is not valid.

The production of secondary electrons generated by carbon nanoparticles and pure water medium irradiated by fast protons is studied by means of model approaches and Monte Carlo simulations. It is demonstrated that due to a prominent collective response to an external field, the nanoparticles embedded in the medium enhance the yield of low-energy electrons. The maximal enhancement is observed for electrons in the energy range where plasmons, which are excited in the nanoparticles, play the dominant role. Electron yield from a solid carbon nanoparticle composed of fullerite, a crystalline form of C60 fullerene, is demonstrated to be several times higher than that from liquid water. Decay of plasmon excitations in carbon-based nanosystems thus represents a mechanism of increase of the low-energy electron yield, similar to the case of sensitizing metal nanoparticles. This observation gives a hint for investigation of novel types of sensitizers to be composed of metallic and organic parts.

Alkalides possess enhanced nonlinear optical (NLO) responses due to localization of excess electrons on alkali metals. We have proposed a new class of alkalides by sandwiching alkali atoms (M) between two Li3O superalkali clusters at MP2/6-311++G(d,p) level. We notice a competition between alkalide characteristics and NLO properties in OLi3-M-Li3O (M=Li, Na and K) isomers. For instance, the atomic charge on M (qM) in D2h structure is -0.58e for M=Li and its first static mean hyperpolarizablity (\b{eta}o) is 1 a.u., but in C2v structure, qM=-0.12e and \b{eta}o= 3.4*103 a.u. More interestingly, the \b{eta}o value for M=K (C2v) increases to 1.9*104 a.u. in which qM=0.24e. These findings may provide new insights into the design of alkalides, an unusual class of salts and consequently, lead to further researches in this direction.

A continuous transition for a system moving in a three-dimensional (3D) space to moving in a lower-dimensional space, 2D or 1D, can be made by means of an external squeezing potential. A squeeze along one direction gives rise to a 3D to 2D transition, whereas a simultaneous squeeze along two directions produces a 3D to 1D transition, without going through an intermediate 2D configuration. In the same way, for a system moving in a 2D space, a squeezing potential along one direction produces a 2D to 1D transition. In this work we investigate the equivalence between this kind of confinement procedure and calculations without an external field, but where the dimension d is taken as a parameter that changes continuously from d=3 to d=1 . The practical case of an external harmonic oscillator squeezing potential acting on a two-body system is investigated in details. For the three transitions considered, 3D~ → ~2D, 2D~ → ~1D, and 3D~ → ~1D, a universal connection between the harmonic oscillator parameter and the dimension d is found. This relation is well established for infinitely large 3D scattering lengths of the two-body potential for 3D~ → ~2D and 3D~ → ~1D transitions, and for infinitely large 2D scattering length for the 2D~ → ~1D case. For finite scattering lengths size corrections must be applied. The traditional wave functions for external squeezing potentials are shown to be uniquely related with the wave functions for specific non-integer dimension parameters, d .

A fundamental theoretical framework is formulated for the investigation of rovibronic spectra resulting from the coupling of molecules to one mode of the radiation field in an optical cavity. The approach involves the computation of (1) cavity-field-dressed rovibronic states, which are hybrid light-matter eigenstates of the `molecule + cavity radiation field' system, and (2) the transition amplitudes between these field-dressed states with respect to a weak probe pulse. The predictions of the theory are shown for the homonuclear Na 2 molecule. The field-dressed rovibronic spectrum demonstrates undoubtedly that the Born--Oppenheimer approximation breaks down in the presence of the cavity radiation field. A clear fingerprint of the strong nonadiabaticity is found, which can only emerge in the close vicinity of conical intersections. In this work, the conical intersection is induced by the quantized radiation field, and it is thus called a "light-induced conical intersection" (LICI). Dependence of the cavity-field-dressed spectrum on the cavity-mode wavelength as well as on the light-matter coupling strength is investigated. Essential changes are identified in the spectra from the weak to the ultrastrong coupling regimes.

Cooper minimum structure of high-order harmonic spectra from atoms or molecules has been extensively studied. In this paper, we demonstrate that the crystal harmonic spectra from an ultrashort mid-infrared laser pulse also exhibit the Cooper minimum characteristic. Based on the accurate band dispersion and k-dependent transition dipole moment (TDM) from the first-principle calculations, it can be found that the harmonic spectra from MgO crystal along {\Gamma}-X direction present a dip structure in the plateau, which is originated from the valley of TDM by examining the distribution of the harmonic intensity at the k-space. The Cooper minimum feature in crystal HHG will pave a new way to retrieve the band information of solid materials by using HHG from the ultrashort mid-infrared laser pulse.

The interaction of a single manganese impurity with silicon is analyzed in a combined experimental and theoretical study of the electronic, magnetic, and structural properties of manganese-doped silicon clusters. The structural transition from exohedral to endohedral doping coincides with a quenching of high-spin states. For all geometric structures investigated, we find a similar dependence of the magnetic moment on the manganese coordination number and nearest neighbor distance. This observation can be generalized to manganese point defects in bulk silicon, whose magnetic moments fall within the observed magnetic-to-nonmagnetic transition, and which therefore react very sensitively to changes in the local geometry. The results indicate that high spin states in manganese-doped silicon could be stabilized by an appropriate lattice expansion.