Generation and orientation of organoxenon molecule H–Xe–CCH in the gas phase

Abstract

The measured low initial sticking probability of oxygen molecules at the Al(111) surface that had puzzled the field for many years was recently explained in a non-adiabatic picture invoking spinselection rules [J. Behler et al., Phys. Rev. Lett. 94, 036104 (2005)]. These selection rules tend to conserve the initial spin-triplet character of the free O2 molecule during the molecule's approach to the surface. A new locally-constrained density-functional theory approach gave access to the corresponding potential-energy surface (PES) seen by such an impinging spin-triplet molecule and indicated barriers to dissociation which reduce the sticking probability. Here, we further substantiate this non-adiabatic picture by providing a detailed account of the employed approach. Building on the previous work, we focus in particular on inaccuracies in present-day exchange-correlation functionals. Our analysis shows that small quantitative differences in the spin-triplet constrained PES obtained with different gradient-corrected functionals have a noticeable effect on the lowest kinetic energy part of the resulting sticking curve.

Matrix-isolation and ab initio study of HXeCCH complexed with acetylene

“…This species can be produced with high yield using UV photolysis or highenergy electron irradiation of H 2 C 2 /Xe matrices. In addition to xenon matrices, it was also characterized in argon and krypton matrices [20] and in xenon clusters in the gas phase [21]. The recent computational estimates show that HXeCCH could be remarkably stable up to room temperature [22].…”

Intermolecular interactions involving noble-gas hydrides: Where the blue shift of vibrational frequency is a normal effect

“…The intense absorption of the H-Ng stretching modes makes these molecules relatively easy to detect in experiments by using infrared (IR) spectroscopy. Most of the experiments with the HNgY molecules have been done in noble-gas matrices; however, recently some of these molecules have been found in gas-phase xenon clusters [22].…”

Lineshape analysis of stimulated Raman spectra of the near‐nozzle region of free jet expansions

“…Among them, highresolution spectroscopic techniques, such as visible absorption, [3] diode-laser infrared absorption, [4,5] Fourier transform infrared (FTIR) absorption spectroscopy, [6,7] Fourier transform microwave (FTMW) measurements, [8] resonance enhanced multiphoton ionization (REMPI), [9,10] cavity ring down spectroscopy, [11] or nonlinear Raman spectroscopies (stimulated Raman Spectroscopy (SRS), CARS, etc), [12,13] have been widely used to measure vibrationrotation spectra of molecules cooled in the expansion and for the analysis of phenomena naturally occurring, or externally induced, in free jets and supersonic beams, like nonequilibrium between the molecular degrees of freedom, [9,10] nucleation and clustering of the gas, [11,12] photodissociation and photon-induced reactions, [14,15] or interactions of molecules with fields. [16] In the spectra obtained from jets with techniques that have a great field depth, like infrared absorption, the measured intensity and the profile of the spectral lines are the result of an integration along the line of sight, containing information about the density, temperature, and velocity of the observed particles within the jet. An inhomogeneous broadening of the lines is thus produced when the expansion is optically probed in a direction perpendicular to the jet axis, where different groups of molecules contribute to the lineshape with a specific Doppler shift and a specific weight given by their number density.…”