Wolfgang Christen

Generation and Propagation of Intense Supersonic Beams

Computer simulations and experiments have been performed to quantify the effects of nozzle shape and skimmer placement on high-density supersonic jets. It is shown that the on axis beam intensity achieved is much higher than intensity achieved using standard sonic nozzles. Changes in skimmer design and positioning are required to allow this intense jet to propagate in a typical supersonic beam setup.

Efficient cooling in supersonic jet expansions of supercritical fluids: CO and CO2.

Pulsed, supersonic beams of pure carbon monoxide and carbon dioxide at stagnation conditions above their critical point have been investigated by time-of-flight measurements as a function of pressure and temperature. Although both molecules form clusters readily in adiabatic expansions, surprisingly large speed ratios (above 100) indicative of very low translational temperatures (below 0.1 K) have been achieved. In particular, the supersonic expansion of CO(2) at stagnation temperatures slightly above the phase transition to the supercritical state results in unprecedented cold beams. This efficient cooling is attributed to the large values of the heat capacity ratio of supercritical fluids in close vicinity of their critical point.

Pulsed supersonic expansion of nonvolatile solids

A compact apparatus for transferring nonvolatile particles into the gas phase and depositing them on a solid surface has been built and tested successfully. As initial experiment, solid caffeine with a vanishingly low vapor pressure has been dissolved in supercritical carbon dioxide, expanded into vacuum using a pulsed, supersonic molecular beam, and detected using a simple residual gas analyzer.

Supersonic Beams at High Particle Densities: Model Description beyond the Ideal Gas Approximation†

Supersonic molecular beams constitute a very powerful technique in modern chemical physics. They offer several unique features such as a directed, collision-free flow of particles, very high luminosity, and an unsurpassed strong adiabatic cooling during the jet expansion. While it is generally recognized that their maximum flow velocity depends on the molecular weight and the temperature of the working fluid in the stagnation reservoir, not a lot is known on the effects of elevated particle densities. Frequently, the characteristics of supersonic beams are treated in diverse approximations of an ideal gas expansion. In these simplified model descriptions, the real gas character of fluid systems is ignored, although particle associations are responsible for fundamental processes such as the formation of clusters, both in the reservoir at increased densities and during the jet expansion. In this contribution, the various assumptions of ideal gas treatments of supersonic beams and their shortcomings are reviewed. It is shown in detail that a straightforward thermodynamic approach considering the initial and final enthalpy is capable of characterizing the terminal mean beam velocity, even at the liquid-vapor phase boundary and the critical point. Fluid properties are obtained using the most accurate equations of state available at present. This procedure provides the opportunity to naturally include the dramatic effects of nonideal gas behavior for a large variety of fluid systems. Besides the prediction of the terminal flow velocity, thermodynamic models of isentropic jet expansions permit an estimate of the upper limit of the beam temperature and the amount of condensation in the beam. These descriptions can even be extended to include spinodal decomposition processes, thus providing a generally applicable tool for investigating the two-phase region of high supersaturations not easily accessible otherwise.

Precision velocity measurements of pulsed supersonic jets.

We introduce a straightforward experimental approach for determining the mean flow velocity of a supersonic jet with very high precision. While time measurements easily can achieve accuracies of Δt/t ≤ 10(-4), typically the absolute flight distances are much less well-defined. This causes significantly increased errors in calculations of the mean flow velocity and mean kinetic energy. The basic concept to improve on this situation is changing the flight distance in vacuo by precisely defined increments employing a linear translation stage. We demonstrate the performance of this method with a flight path that can be varied by approximately 15% with a tolerance of setting of 50 μm. In doing so, an unprecedented accurate value for the mean flow velocity of Δv/ < 3 × 10(-4) has been obtained without prior knowledge of the total distance. This very high precision in source pressure, temperature, and particle speed facilitates an improved energetic analysis of condensation processes in supersonic jet expansions. The technique is also of broad interest to other fields employing the strong adiabatic cooling of supersonic beams, in particular, molecular spectroscopy. In the presented case study, a thorough analysis of arrival time spectra of neutral helium implies cluster formation even at elevated temperatures.

Probing free jet expansions of supercritical fluids

Attempting to improve the comprehension of supersonic molecular beams at elevated pressures we present a comparative study of thermodynamic descriptions of the terminal flow velocity in free jet expansions. As model system we choose carbon dioxide due to its widespread utilization in supercritical fluid technology. Numerical results for the thermodynamic quantities are obtained using a high accuracy equation of state explicit in the Helmholtz free energy. The influence of pressure and temperature on the beam velocity is investigated for a broad range of stagnation conditions. A consistent physical picture is obtained for calculations employing the initial and final molar enthalpies, while enormous discrepancies are found for descriptions based on the molar isobaric heat capacity or the heat capacity ratio. The deviations are particularly pronounced at the gas‐liquid phase transition and in the vicinity of the critical point and can be related to the diverse assumptions of ideal gas behavior. It is shown that computations using real fluid enthalpies permit to assess the fraction of condensation in supersonic jets.

Apparatus for reactive cluster-surface studies

We present a new instrument that has been specifically designed for systematic studies of reactive cluster-surface collisions under well-defined ultrahigh-vacuum conditions. As a key feature, it incorporates a temperature-controlled, high-pressure cluster source with an unsurpassed pulse-to-pulse stability for the generation of weakly bound molecular aggregates. Impact processes can be investigated in two experimental configurations complementing one another: In the first, the exploration of intracluster reactions of accelerated, size-selected, positively or negatively charged cluster ions (1–100eV∕molecule) is accomplished, employing an inert target surface combined with angular-integrated ion detection. This arrangement uses a compact, homebuilt dual time-of-flight mass spectrometer with excellent mass resolution m∕Δm>2000 and postacceleration capabilities. In the second configuration, the detailed analysis of chemical reactions between neutral clusters and a well-defined single crystal at lower kinetic...

Ultra-precise particle velocities in pulsed supersonic beams

We describe an improved experimental method for the generation of cold, directed particle bunches, and the highly accurate determination of their velocities in a pulsed supersonic beam, allowing for high-resolution experiments of atoms, molecules, and clusters. It is characterized by a pulsed high pressure jet source with high brilliance and optimum repeatability, a flight distance of few metres that can be varied with a tolerance of setting of 50 μm, and a precision in the mean flight time of particles of better than 10(-4). The technique achieves unmatched accuracies in particle velocities and kinetic energies and also permits the reliable determination of enthalpy changes with very high precision.

Precise thermodynamic control of high pressure jet expansions

We describe an experimental setup for supersonic jet expansions of supercritical fluids. It is characterized by well-defined thermodynamic values to allow systematic investigations of pressure and temperature effects on molecular beam parameters. The design permits stagnation temperatures T(0)=225-425 K with a thermal stability DeltaT(0)<30 mK and stagnation pressures p(0)=0.2-12 MPa that are measured with 0.05% precision. For optimum stability, gas reservoir, pressure transducer, and gauge amplifier are temperature-controlled, and a feedback loop permits active pressure stabilization using a pulseless syringe pump. With this approach stagnation pressures can be reproduced and kept constant to Deltap(0)<2.9 kPa. As a result, flow velocity and kinetic energy of molecular beams can be controlled with maximum accuracy.

Quantitative Study of 4He Real Gas Effects Using Supersonic Beams

Abstract The experimental realization of accurately defined source conditions, combined with an undisturbed flight path of precisely known length, permits the generation of supersonic molecular beams with an extremely well characterized axial velocity distribution. This achievement can be used for a quantitative assessment of theoretical models of condensation during the jet expansion, based on high accuracy equations of state. For helium-4, which is commonly put on a level with the ideal gas, we contrast two empirical equations of state with respect to enthalpy changes. These can be validated through a comparison with experimentally determined mean terminal flow velocities. At cryogenic temperatures, strong deviations from the ideal gas behavior are observed. Most notably, even the differences between the predictions of the two fundamental equations are large enough to be distinguished by high-resolution time-of-flight measurements.