Physics

Supersonic helium beams are used in a wide range of applications, for example surface scattering experiments and, most recently, microscopy. The high ionization potential of neutral helium atoms makes it difficult to build efficient detectors. Therefore, it is important to develop beam sources with a high centre line intensity. Several approaches for predicting the centre line intensity exist, with the quitting surface model incorporating the largest amount of physical dependencies. However, until now only a limited amount of experimental data has been available. Here we present a study where we compare the quitting surface model with an extensive set of experimental data. In the quitting surface model the source is described as a sphere from where the particles leave in a molecular flow determined by Maxwell-Boltzmann statistics. We use numerical solutions of the Boltzmann equation to determine its properties. The centre-line intensity is then calculated using an analytical integral. This integral can be reduced to two cases, one which assumes a continuously expanding beam until the skimmer aperture, and another which assumes a quitting surface placed before the aperture. We compare the two cases to experimental data with a nozzle diameter of 10 micron, skimmer diameters ranging from 4 micron to 390 micron, a source pressure range from 2 to 190 bar, and nozzle-skimmer distances between 17.3 mm and 5.3 mm. To support the two analytical approaches, we have also performed equivalent ray tracing simulations. We conclude that the quitting surface model predicts the centre line intensity well for skimmers with a diameter larger than 120 micron when using a beam expanding until the skimmer aperture. For the case of smaller skimmers the trend is correct, but the absolute agreement not as good. We propose several explanations for this, and test the ones that can be implemented analytically.

Cs 2 Rydberg-ground molecules consisting of a Rydberg, n D J (33 ≤ n ≤ 39), and a ground state atom, 6 S 1/2 (F= 3 or 4 ) , are investigated by photo-association spectroscopy in a cold atomic gas. We observe vibrational spectra that correspond to triplet T Σ and mixed S,T Σ molecular states. We establish scaling laws for the energies of the lowest vibrational states vs principal quantum number and obtain zero-energy singlet and triplet s -wave scattering lengths from experimental data and a Fermi model. Line broadening in electric fields reveals the permanent molecular electric-dipole moments; measured values agree well with calculations. We discuss the negative polarity of the dipole moments, which differs from previously reported cases.

The infrared spectra of the weakly-bound dimers OCS-HCCCCH, in the region of the nu1 fundamental band of OCS (2050 cm-1), and N2O-HCCCCH, in the region of the nu1 fundamental band of N2O (2200 cm-1), were observed in a pulsed supersonic slit jet expansion probed with tunable diode/QCL lasers. Both OCS-HCCCCH and N2O-HCCCCH were found to have planar structure with side-by-side monomer units having nearly parallel axes. These bands have hybrid rotational structure which allows for estimates of the orientation of OCS and N2O in the plane of their respective dimers. Analogous bands for OCS-DCCCCD and N2O-DCCCCD were also observed and found to be consistent with the normal isotopologues. Various levels of ab initio calculations were performed to find stationary points on the potential energy surface, optimized structures and interaction energies. Four stable geometries were found for OCS-HCCCCH and three for N2O-HCCCCH. The rotational parameters at CCSD(T*)-F12c level of theory give results in very good agreement with those obtained from the observed spectra. In both dimers, the experimental structure corresponds to the lowest energy isomer.

Atoms and molecules attached to rare gas clusters are ionized by an interatomic autoionization process traditionally termed 'Penning ionization' when the host cluster is resonantly excited. Here we analyze this process in the light of the interatomic Coulombic decay (ICD) mechanism, which usually contains a contribution from charge exchange at short interatomic distance, and one from virtual photon transfer at large interatomic distance. For helium (He) nanodroplets doped with alkali metal atoms (Li, Rb), we show that long-range and short-range contributions to the interatomic autoionization can be clearly distinguished by detecting electrons and ions in coincidence. Surprisingly, ab initio calculations show that even for alkali metal atoms floating in dimples at large distance from the nanodroplet surface, autoionization is largely dominated by charge exchange ICD. Furthermore, the measured electron spectra manifest ultrafast internal relaxation of the droplet into mainly the 1s2s 1^S state and partially into the metastable 1s2s 3^S state.

We present a combined experimental and theoretical study of the charging dynamics of helium nanodroplets doped with atoms of different species and irradiated by intense near-infrared (NIR) laser pulses (<10^15 Wcm-2). In particular, we elucidate the interplay of dopant ionization inducing the ignition of a helium nanoplasma, and the charging of the dopant atoms driven by the ionized helium host. Most efficient nanoplasma ignition and charging is found when doping helium droplets with xenon atoms, in which case high charge states both of helium (He2+) and of xenon (Xe^21+) are detected. In contrast, only low charge states of helium and dopants are measured when doping with potassium and calcium atoms. Classical molecular dynamics simulations which include focal averaging generally reproduce the experimental results and provide detailed insights into the correlated charging dynamics of guest and host clusters.

We introduce chiral rotational spectroscopy: a new technique that enables the determination of the orientated optical activity pseudotensor components B XX , B YY and B ZZ of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centres. The principles that underpin chiral rotational spectroscopy could be exploited moreover in the search for molecular chirality in space, which, if found, might add weight to hypotheses that biological homochirality and indeed life itself are of cosmic origin. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarisability components α XX , α YY and α ZZ as by-products, which could see it find use even for achiral molecules.

ClasSOMfier is a software package to classify atoms into a given number of disconnected groups (or clusters) and detect lattice defects, such as vacancies, interstitials, dislocations, voids and grain boundaries. Each cluster is formed by atoms whose atomic environment can be described by a common pattern. Unlike many methods available in the literature, where these patterns are given in advance and are associated with known lattice structures (i.e. fcc, bcc or hcp), this code implements a Kohonen network, which is based on unsupervised learning and where no information about the atomic environment has to be given in advance. ClasSOMfier accelerates the application of machine learning for cluster analysis by providing an efficient and fast code in Fortran with a user-friendly interface in Python.

We present the results of classical molecular dynamics simulations of collision-induced fusion and fragmentation of C 60 fullerenes, performed by means of the MBN Explorer software package. The simulations provide information on structural differences of the fused compound depending on kinematics of the collision process. The analysis of fragmentation dynamics at different initial conditions shows that the size distributions of produced molecular fragments are peaked for dimers, which is in agreement with a well-established mechanism of C 60 fragmentation via preferential C 2 emission. Atomic trajectories of the colliding particles are analyzed and different fragmentation patterns are observed and discussed. On the basis of the performed simulations, characteristic time of C 2 emission is estimated as a function of collision energy. The results are compared with experimental time-of-flight distributions of molecular fragments and with earlier theoretical studies. Considering the widely explored case study of C 60 --C 60 collisions, we demonstrate broad capabilities of the MBN Explorer software, which can be utilized for studying collisions of a broad variety of nanoscale and biomolecular systems by means of classical molecular dynamics.

Cluster size distributions were investigated in case of different nozzle geometries in argon and xenon using Rayleigh scattering diagnostics. Different nozzle geometries result in different behaviour, therefore both spatial- and temporal cluster size distributions were studied to obtain a well-characterized cluster target. It is shown that the generally used Hagena scaling can result in a significant deviation from the observed data and the behaviour cannot be described by a single material condensation parameter. The results along with the nanoplasma model applied to the data of previous high harmonic generation experiments allow the independent measurement of cluster size and cluster density.

For the asymmetric spherical dimer of an endohedrally confined atom and a host fullerene, an innershell vacancy of either system can decay through the continuum of an outer electron hybridized between the systems. Such decays, viewed as coherent superpositions of the single-center Auger and two-center inter-Coulombic (ICD) amplitudes, are found to govern leading decay mechanisms in noble-gas endofullerenes, and are likely omnipresent in this class of nanomolecules. A comparison between resulting autoionizing resonances calculated in the photoionization of Ar@C60 and Kr@C60 exhibits details of the underlying processes.