M. Abu-samha

The local structure of small water clusters: imprints on the core-level photoelectron spectrum

We report on an O 1s photoelectron-spectroscopy study of small neutral water clusters produced by adiabatic expansion. The photoelectron spectra were acquired under two different experimental conditions. At intermediate resolution, the cluster signal was characterized by a very broad O 1s peak with a flat top. In the second set of measurements, resolution was significantly increased at the cost of lower count rates. The cluster signal was now partly resolved into a bimodal structure. Extensive theoretical calculations were undertaken to facilitate an interpretation of the spectrum. These results suggest that the bimodal feature may be ascribed to ionization of water molecules in different hydrogen-bonding configurations, more specifically, molecules characterized by donation of either one or both hydrogen atoms in H-bonding.

Surface relaxation in water clusters: Evidence from theoretical analysis of the oxygen 1s photoelectron spectrum

We present a theoretical interpretation of the oxygen 1s photoelectron spectrum published by Ohrwall et al. [J. Chem. Phys. 123, 054310 (2005)]. A water cluster that contains 200 molecules was simulated at 215 K using the polarizable AMOEBA force field. The force field predicts longer O...O distances at the cluster surface than in the bulk. Comparisons to ab initio molecular dynamics (MD) simulations indicate that the force field underestimates the degree of surface relaxation. By comparing cluster lineshape models, computed from MD simulations, to the experimental spectrum we find further evidence of surface relaxation.

Size of neutral argon clusters from core-level photoelectron spectroscopy

Theoretical models of lineshapes in Ar2p photoionization spectra have been calculated for free, neutral argon clusters of different sizes. The lineshape models are fitted to experimental spectra and used to estimate the mean cluster size realized in the experiment. The results indicate that size estimators working from stagnation conditions [R. Karnbach, M. Joppien, J. Stapelfeldt, J. Wörmer and T.Möller, Rev. Sci. Instrum., 1993, 64, 2838] may underestimate the mean cluster size.

Two size regimes of methanol clusters produced by adiabatic expansion

Free neutral methanol clusters produced by adiabatic expansion have been studied by photoelectron spectroscopy and line shape modeling. The results show that clusters belonging to two distinct size regimes can be produced by changing the expansion conditions. While the larger size regime can be well described by line shapes calculated for clusters consisting of hundreds of molecules, the smaller size regime corresponds to methanol oligomers, predominantly of cyclic structure. There is little contribution from dimers to the spectra.

Interrogation of orbital structure by elliptically polarized intense femtosecond laser pulses

We solve the three-dimensional time-dependent Schroedinger equation and present investigations of the imprint of the orbital angular node in photoelectron momentum distributions of an aligned atomic p-type orbital following ionization by an intense elliptically polarized laser pulse of femtosecond duration. We investigate the role of light ellipticity and the alignment angle of the major polarization axis of the external field relative to the probed orbital by studying radial and angular momentum distributions, the latter at a fixed narrow interval of final momenta close to the peak of the photoelectron momentum distribution. In general only the angular distributions carry a clear signature of the orbital symmetry. Our study shows that circular polarization gives the most clear imprints of orbital nodes. These findings are insensitive to pulse duration.

From multiphoton to tunnelling ionization of neon and argon

We present a theoretical analysis of the longitudinal momentum distribution for Ne and Ar, from the multiphoton to the tunnelling ionization regime. Our theoretical models reproduce recent experimental measurements very well. We find evidence for resonant ionization in the multiphoton regime. In the tunnelling regime, on the other hand, resonant ionization is not active and direct ionization does contribute to the bimodal structure in the momentum distribution of Ne.

Formation and Growth of Clusters of Sulfur Dioxide

Formation and growth of neutral SO2 clusters is investigated in an adiabatic-expansion setup by means of sulfur 2p (S2p) photoelectron spectroscopy and theoretical modeling. The shift in S2p ionization energy between the cluster and a single molecule, i.e., IE(cluster)-IE(monomer), is recorded and used to monitor the mean cluster size over a wide range of expansion conditions. The produced clusters were shown to fall into two different size regimes. Comparison between theoretical simulations and experimental observations suggests that while the smallest clusters belong to the ultrafine particle mode and have a liquid-like structure, the larger clusters belong to the accumulation mode of fine particles and possibly have a frozen cluster core. The transition between the two size/structure regimes occurs over a narrow interval in expansion conditions and may possibly reflect a change in growth mechanism from monomer addition to growth by cluster-cluster collisions. (c) Jarle Harnes, Mahmoud Abu-Samha, Mathias Winkler, and Knut J. Børve

Effective attenuation length from core-level photoelectron spectroscopy of CS2 clusters

The effective attenuation length (λ) is determined to 5.7 ± 1.1 A at an electronic kinetic energy of 30 eV for carbon disulfide, CS2, from sulphur 2p photoelectron spectroscopy and lineshape modelling of CS2 clusters at a temperature of 150–170 K. The present approach is based on exploring the relation between λ and the cluster–monomer chemical shift and width of the cluster peak. A priori knowledge of the cluster temperature is required.

HCl dissociation in methanol clusters from ab initio molecular dynamics simulations and inner-shell photoelectron spectroscopy.

HCl dissociation in methanol clusters is studied by ab initio molecular dynamics simulations and experimentally by X-ray photoelectron spectroscopy. From theoretical simulations of HCl in oligomers and medium-sized clusters of methanol, two states of solvation are identified for HCl: an intermediate proton-sharing (ion pair) state and a fully dissociated state. Lowering the temperature from 150 to 100 K is found to promote full dissociation over the proton-sharing state. The dissociation of HCl is well reflected in the experimental chlorine 2p photoelectron spectrum recorded for a beam of clusters formed by adiabatic expansion of the vapor over a solution of HCl in methanol. In order to reproduce the observed Cl 2p spectrum by means of theoretical line-shape modeling, one needs to take into account both the intermediate proton-sharing state and the fully dissociated state.

Momentum distributions of selected rare-gas atoms probed by intense femtosecond laser pulses

We provide a direct comparison between numerical and experimental (Rudenko et al 2004 J. Phys. B: At. Mol. Opt. Phys. 37 L407) photoelectron momentum distributions in strong-field ionization of selected rare-gas atoms (He, Ne and Ar), probed by femtosecond linearly polarized laser pulses. The calculations are performed by solving the time-dependent Schrodinger equation within the single-active-electron approximation, and focal-volume effects are taken into account by appropriately averaging the results. The resulting momentum distributions are in quantitative agreement with the experimental measurements.