Physics

Dipolar dissociation processes in the electron collisions with carbon monoxide have been studied using time of flight (TOF) mass spectroscopy in combination with the highly differential velocity slice imaging (VSI) technique. Probing ion-pair states both positive and/or negative ions may be detected. The ion yield curve of negative ions provides the threshold energy for the ion-pair production. On the other hand, the kinetic energy distributions and angular distributions of the fragment anion provide detailed dynamics of the dipolar dissociation process. Two ion-pair states have been identified based on angular distribution measurements using VSI technique.

The dipolar dissociation of molecular oxygen due to 21-35 eV energy electron collision has been studied using the time sliced velocity map imaging technique. A rough estimation about the threshold of the process and the kinetic energy and angular distribution of the fragment negative ions are measured. The dipolar dissociation found to be occur due to pre-dissociation of a Rydberg state via ion-pair state for lower incident electron energies as well from also direct excitation to the ion-pair states for relatively higher primary beam energy. The location and symmetry of the excited states were determined from the kinetic energy and angular distribution data respectively.

The non-relativistic three-body Schrödinger equation of the heteronuclear molecular ion HD + is solved in perimetric coordinates using the Lagrange-mesh method. Energies and wave functions of the four lowest vibrational bound or quasibound states v=0−3 are calculated for total orbital momenta from 0 to 47. Energies are given with an accuracy from about 12 digits for the lowest vibrational level to at least 9 digits for the third vibrational excited level. With a simple calculation using the corresponding wave functions, accurate dipole transition probabilities per time unit between those levels are given over the whole v=0−3 rotational bands. Results are presented with six significant figures.

Long-range intermolecular forces are able to steer polar molecules submerged in superfluid helium nanodroplets into highly polar metastable configurations. We demonstrate that the presence of such special structures can be identified, in a direct and determinative way, by electrostatic deflection of the doped nanodroplet beam. The measurement also establishes the structures' electric dipole moments. In consequence, the introduced approach is complementary to spectroscopic studies of low-temperature molecular assembly reactions. It is enabled by the fact that within the cold superfluid matrix the molecular dipoles become nearly completely oriented by the applied electric field. As a result, the massive (tens of thousands of helium atoms) nanodroplets undergo significant deflections. The method is illustrated here by an application to dimers and trimers of dimethyl sulfoxide (DMSO) molecules. We interpret the experimental results with ab initio theory, mapping the potential energy surface of DMSO complexes and simulating their low temperature aggregation dynamics.

We present the first measurements of photoelectron spectra of atomic clusters embedded in superfluid helium (He) nanodroplets. Owing to the large absorption cross section of xenon (Xe) around 100 eV photon energy (4d inner-shell ionization), direct dopant photoionization exceeds charge transfer ionization via the ionized He droplets. Despite the predominant creation of Xe^2+ and Xe^3+ by subsequent Auger decay of free Xe atoms, for Xe embedded in He droplets only singly charged Xe_k^+, k=1,2,3 fragments are observed. Broad Xe^+ ion kinetic-energy distributions indicate Coulomb explosion of the ions due to electron transfer to the primary Auger ions from surrounding neutral atoms. The electron spectra correlated with Xe ions emitted from the He nanodroplets contain a low-energy feature and nearly unshifted Xe photolines. These results pave the way to extreme ultraviolet (XUV) and x-ray photoelectron spectroscopy of clusters and molecular complexes embedded in He nanodroplets.

We report on the experimental observation of interatomic Coulombic decay (ICD) in pure 4 He nanoclusters of mean sizes between N≈ 5000 and 30000 and the subsequent scattering of energetic He + fragments inside the neutral cluster by using cold target recoil ion momentum spectroscopy. ICD is induced in He clusters by using vacuum ultraviolet light of hν= 67 eV from the BESSY II synchrotron. The electronic decay creates two neighboring ions in the cluster at a well-defined distance. The measured fragment energies and angular correlations show that a main energy loss mechanism of these ions inside the cluster is a single hard binary collision with one atom of the cluster.

Nonadiabatic effects are ubiquitous in physics, chemistry and biology. They are strongly amplified by conical intersections (CIs) which are degeneracies between electronic states of triatomic or larger molecules. A few years ago it has been revealed that CIs in molecular systems can be formed by laser light even in diatomics. Due to the prevailing strong nonadiabatic couplings, the existence of such laser-induced conical intersections (LICIs) may considerably change the dynamical behavior of molecular systems. By analyzing the photodissociation process of the D2+ molecule carefully, we found a robust effect in the angular distribution of the photofragments which serves as a direct signature of the LICI providing undoubted evidence for its existence.

Angular resolved electron energy-loss spectroscopy (EELS) gives access to the momentum and the energy dispersion of electronic excitations and allows to explore the transition from individual to collective excitations. Dimensionality and geometry play thereby a key role. As a prototypical example we analyze theoretically the case of Buckminster fullerene C60 using ab initio calculations based on the time-dependent density-functional theory. Utilizing the non-negative matrix factorization method, multipole contributions to various collective modes are isolated, imaged in real space, and their energy and momentum dependencies are traced. A possible experiment is suggested to access the multipolar excitations selectively via EELS with electron vortex (twisted) beams. Furthermore, we construct an accurate analytical model for the response function. Both the model and the ab initio cross sections are in excellent agreement with recent experimental data.

Universality in fragmentation has been the framework of scientific interest from a considerable period to disentangle the structure and dynamics of atoms and molecules. Studies in this direction however are still elusive to explore the details about polyatomic molecules because of their complexity in structure and electron-electron correlations. Hence many-body fragmentation dynamics of polyatomic hydrogen peroxide (H2O2) that plays a decisive role in atmospheric physics and chemistry and indeed which has been discovered recently in interstellar medium, is reported here. The three-body dissociation of H2O23+ which forms the main subject of this article discusses here particularly about the sequential and non-sequential fragmentation pathways and cis- and trans-isomerism that takes place in H2O2. In addition to these details, the article also includes four-body dissociation dynamics of H2O24+/5+ that has been employed to investigate the structural-chirality in H2O2.

The process of wave propagation in an infinite linear chain is analyzed. Established, that dispersion relation between the angular frequency and the wave number for transverse waves differs from similar dependencies for longitudinal.