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A novel dual time-of-flight imaging analyzer has been developed for studies of gas phase reactions and the scattering or desorption of ions and molecules from surfaces. The analyzer is capable of experimentally selecting a two-dimensional slice of particles from a three-dimensional flux without the necessity for deconvolution of the resulting velocity images by the Abel transform. The analyzer operates through ionization of the scattered species and their subsequent flight through a field-free region. This initial flight allows a dispersion according to the species natural velocity distribution. The second time of flight deflects the ions through a right angle and through a flight tube allowing dispersion according to mass or charge before detection. The analyzer offers two modes of operation — the first of these produces a mass spectrum of the desorbing species, the second produces a two-dimensional velocity map of the desorbing species. Trial results using an effusive beam source and acetone as a test gas have demonstrated the operation of the analyzer. The operation of the analyzer has been simulated and optimized to reduce ion flight aberrations. A set of orthogonal two-dimensional polynomial functions have been derived to reduce residual aberrations across a broad range of operating conditions. An upper limit to the temporal resolution of the analyzer has been established and a set of working parameters for low distortion electron beam ionization have been presented.

The gas phase reaction thermodynamics in the chemical vapor deposition (CVD) process of preparing boron carbides via the precursors of BCl₃–C₃H₆(propene)–H₂ is investigated with a set of 325 gaseous species, in which the data for 135 species are evaluated in this work. The thermochemistry data are calculated with accurate model chemistry at G3(MP2) and G3//B3LYP levels. The concentration distribution of all of the 325 species is obtained with the principle of chemical equilibrium. The thermochemistry data include the heat capacities, entropies, enthalpies of formation, and Gibbs free energies of formation. The heat capacities and entropies at temperatures in 298.15–2000 K are evaluated with the standard statistical thermodynamics. The Gibbs free energies of formation in 298.15–2000 K are calculated with the classical thermodynamics based on the developed heat capacities and entropies. By including the crystal B₄C, C(graphite), and B, the results for an example of the 3:1:2 precursors of BCl₃:C₃H₆:H₂ show that the crystal B₄C can be produced at temperatures higher than 700 K while the graphite has a higher molar value and can be produced at lower temperatures. It is also examined that the production of graphite can be controlled by changing the ratio of the injected reactants or pressure. It is interesting that BHCl₂, BCH₃Cl₂, BH₂Cl, and B₂Cl₄ are found to be the most effective species in the CVD process, which is similar to those in the BCl₃–CH₄–H₂ system. The results predicted in this work are consistent with the experiments.

This work consists of an investigation, using current methods of quantum chemistry and, at first, on the basis of the available experimental results, about the new mechanisms of the reaction between ozone and hydrogen cyanide (HCN) in gaseous phases. Three possible reaction pathways which we have determined as the most probable and, all three, leading exactly to the same products, are proposed here. For each of these pathways, several steps for which we performed a kinetic study were identified in the singlet potential energy surface. To confirm the proposed mechanisms, we have achieved a study including the intrinsic reaction coordinate (IRC), the topological analysis of atoms in molecule and the harmonic vibrational frequencies calculations. The obtained results reveal that the final products have considerable thermodynamic stability and this reaction is exothermic in standard conditions.

We will present resonant two-photon ionization spectra for meso-tetraphenylporphyrin, H₂TPP, measured under isolated conditions. The polycrystalline compound was vaporized, in vacuo, using both thermal and laser desorption, and seeded into a supersonic expansion of an inert-carrier gas. The molecules remain largely intact in the gaseous phase. However, the two techniques for vaporizing H₂TPP give different internal temperatures for the isolated substrate, with greater vibrational cooling achieved using laser desorption. A comparison of the peak positions and intensities in the resonant two-photon ionization spectra of thermal- and laser-desorbed molecules provides an insight into the vibrational structure of the Q band. In particular, the greater contribution made by electronic transitions originating from higher vibrational levels in the ground state of H₂TPP is emphasized. We conclude that vibronic coupling in the ground electronic state plays an important role in a quantum-mechanical interpretation of the Q band.

In the current work, the structure of the enzyme CC chemokine eotaxin-3 (1G2S) was chosen as a case study to investigate the effects of gas phase on the predicted protein conformation using molecular dynamics simulation. Generally, simulating proteins in the gas phase tend to suffer from various drawbacks, among which excessive numbers of protein-protein hydrogen bonds. However, current results showed that the effects of gas phase simulation on 1G2S did not amplify the protein-protein hydrogen bonds. It was also found that some of the hydrogen bonds which were crucial in maintaining the secondary structural elements were disrupted. The predicted models showed high values of RMSD, 11.5 Å and 13.5 Å for both vacuum and explicit solvent simulations, respectively, indicating that the conformers were very much different from the native conformation. Even though the RMSD value for the in vacuo model was slightly lower, it somehow suffered from lower fraction of native contacts, poor hydrogen bonding networks and fewer occurrences of secondary structural elements compared to the solvated model. This finding supports the notion that water plays a dominant role in guiding the protein to fold along the correct path.

In this contribution, we discuss aspects of spectral tuning of molecular chromophores at the atomic level. The basis for the discussion is a series of measurements performed at the electrostatic ion-storage ring ELISA at the University of Aarhus. The experimental technique, which is a type of “action spectroscopy” based on photo dissociation, will briefly be discussed. We will present examples of spectral tuning due to external charges and proton exchange with the hosting medium.