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We demonstrate liquid-jet photoelectron spectroscopy from a flatjet formed by the impingement of two micron-sized cylindrical jets of different aqueous solutions. Flatjets provide flexible experimental templates enabling unique liquid-phase experiments that would not be possible using single cylindrical liquid jets. One such possibility is to generate two co-flowing liquid-jet sheets with a common interface in vacuum, with each surface facing the vacuum being representative of one of the solutions, allowing face-sensitive detection by photoelectron spectroscopy. The impingement of two cylindrical jets also enables the application of different bias potentials to each jet with the principal possibility to generate a potential gradient between the two solution phases. This is shown for the case of a flatjet composed of a sodium iodide aqueous solution and neat liquid water. The implications of asymmetric biasing for flatjet photoelectron spectroscopy are discussed. The first photoemission spectra for a sandwich-type flatjet comprised of a water layer encapsulated by two outer layers of an organic solvent (toluene) are also shown. [ABSTRACT FROM AUTHOR]

We present spatially resolved measurements of the temperature of a flat liquid water microjet for varying ambient pressures, from vacuum to 100% relative humidity. The entire jet surface is probed in a single shot by a high-resolution infrared camera. Obtained 2D images are substantially influenced by the temperature of the apparatus on the opposite side of the infrared camera; a protocol to correct for the thermal background radiation is presented. In vacuum, we observe cooling rates due to water evaporation on the order of 105 K/s. For our system, this corresponds to a temperature decrease in approximately 15 K between upstream and downstream positions of the flowing leaf. Making reasonable assumptions on the absorption of the thermal background radiation in the flatjet, we can extend our analysis to infer a thickness map. For a reference system, our value for the thickness is in good agreement with the one reported from white light interferometry. [ABSTRACT FROM AUTHOR]

We present a unique experimental design that enables the measurement of photoelectron circular dichroism (PECD) from chiral molecules in aqueous solution. The effect is revealed from the intensity difference of photoelectron emission into a backward-scattering angle relative to the photon propagation direction when ionizing with circularly polarized light of different helicity. This leads to asymmetries (normalized intensity differences) that depend on the handedness of the chiral sample and exceed the ones in conventional dichroic mechanisms by orders of magnitude. The asymmetry is largest for photon energies within several electron volts above the ionization threshold. A primary aim is to explore the effect of hydration on PECD. The modular and flexible design of our experimental setup EASI (Electronic structure from Aqueous Solutions and Interfaces) also allows for detection of more common photoelectron angular distributions, requiring distinctively different detection geometries and typically using linearly polarized light. A microjet is used for liquid-sample delivery. We describe EASI's technical features and present two selected experimental results, one based on synchrotron-light measurements and the other performed in the laboratory, using monochromatized He-II α radiation. The former demonstrates the principal effectiveness of PECD detection, illustrated for prototypic gas-phase fenchone. We also discuss the first data from liquid fenchone. In the second example, we present valence photoelectron spectra from liquid water and NaI aqueous solution, here obtained from a planar-surface microjet (flatjet). This new development features a more favorable symmetry for angle-dependent photoelectron measurements. [ABSTRACT FROM AUTHOR]

We report on rotationally resolved laser induced fluorescence (LIF) and vibrationally resolved resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the chiral molecule 1-indanol. Spectra of the S1 ← S0 electronic transition are recorded in a jet-cooled, pulsed molecular beam. Using two time-delayed pulsed lasers, the lifetimes of the S1 state of the two most stable conformers, referred to as eq1 and ax2, have been determined. The S1 ← S0 origin bands of these conformers as well as the transition to a vibrationally excited level in the S1 state of eq1 are recorded with full rotational resolution (25 MHz observed linewidth) by measuring the LIF intensity following excitation with a tuneable, narrowband cw laser. On selected rotationally resolved electronic transitions, Lamb-dips are measured to confirm the Lorentzian lifetime-contribution to the observed lineshapes. The rotationally resolved S1 ← S0 origin band of a neon-complex of eq1 is measured via LIF as well. The fit of the rotationally resolved LIF spectra of the origin bands to those of an asymmetric rotor yields a standard deviation of about 6 MHz. The resulting spectroscopic parameters are tabulated and compared to the outcome of ab initio calculations. For both conformers as well as for the Ne-eq1 complex, the geometric structures in the S0 and S1 states are discussed. For all systems, the transition dipole moment is mainly along the a-axis, the contributions along the b- and c-axes being about one order of magnitude smaller. [ABSTRACT FROM AUTHOR]

Supersonic beams of polar molecules are deflected using inhomogeneous electric fields. The quantum-state selectivity of the deflection is used to spatially separate molecules according to their quantum state. A detailed analysis of the deflection and the obtained quantum-state selection is presented. The rotational temperatures of the molecular beams are determined from the spatial beam profiles and are all approximately 1 K. Unprecedented degrees of laser-induced alignment (2 θ2D>=0.972) and orientation of iodobenzene molecules are demonstrated when the state-selected samples are used. Such state-selected and oriented molecules provide unique possibilities for many novel experiments in chemistry and physics. [ABSTRACT FROM AUTHOR]

We report on the design and characterization of a new apparatus for performing quantum-state resolved surface scattering experiments. The apparatus combines optical state-specific molecule preparation with a compact hexapole and a Stark decelerator to prepare carrier gas-free pulses of quantum-state pure CO molecules with velocities controllable between 33 and 1000 m/s with extremely narrow velocity distributions. The ultrahigh vacuum surface scattering chamber includes homebuilt ion and electron detectors, a closed-cycle helium cooled single crystal sample mount capable of tuning surface temperature between 19 and 1337 K, a Kelvin probe for non-destructive work function measurements, a precision leak valve manifold for targeted adsorbate deposition, an inexpensive quadrupole mass spectrometer modified to perform high resolution temperature programmed desorption experiments and facilities to clean and characterize the surface. [ABSTRACT FROM AUTHOR]

We have combined a Stark decelerator with a molecular beam-surface scattering setup to accurately measure the absolute electron emission yield, γ, of CO (a3Π) quenching at a Au(111) surface with quantum state resolution. We clearly observe an enhanced probability of electron emission when scattering vibrationally excited states of CO from the surface. [ABSTRACT FROM AUTHOR]

The Stark deceleration method exploits the concepts of charged particle accelerator physics to produce molecular beams with a tunable velocity. These tamed molecular beams offer interesting perspectives for precise crossed beam scattering studies as a function of the collision energy. The method has advanced sufficiently to compete with state-of-the-art beam methods that are used for scattering studies throughout. This is demonstrated here for the scattering of OH radicals (X2Π3/2, J= 3/2, f) with Ar atoms, a benchmark system for the scattering of open-shell molecules with atoms. Parity-resolved integral state-to-state inelastic scattering cross sections are measured at collision energies between 80 and 800 cm−1. The threshold behavior and collision energy dependence of 13 inelastic scattering channels is accurately determined. Excellent agreement is obtained with the cross sections predicted by close-coupling scattering calculations based on the most accurate ab initioOH + Ar potential energy surfaces to date. [ABSTRACT FROM AUTHOR]

A high-vacuum gate valve for skimmed molecular-beam experiments is described. It is designed with a very short extent of only 10 mm along the molecular-beam axis to minimize the distance between the molecular-beam source and the experiment to provide the maximum molecular flux to the experiment. At the same time it provides free space on both sides of the skimmer to not disturb the supersonic expansion in front of the skimmer, to give optical access to the full distance between beam source and skimmer, and to allow for placing electrostatic devices very close behind the skimmer. The gate valve allows to maintain high-vacuum conditions (10-8 mbar) in the experimental chamber while the source chamber is brought up to atmospheric pressure for modifications or maintenance. The valve can be operated from outside the vacuum chamber while maintaining vacuum conditions in all chambers. [ABSTRACT FROM AUTHOR]

Focusing of molecular beams using an electrostatic hexapole is a mature technique to produce samples of state-selected molecules. The ability to efficiently focus molecules depends on the properties of the molecular species of interest, the length of the hexapole state selector, as well as on the maximum electric field strength that can be achieved in these devices. In particular for species with a small effective dipole moment such as nitric oxide (NO), hexapole state selectors of several meters in length are required to focus the beam. We report on a novel design for an electrostatic hexapole state-selector that allows for a maximum electric field strength of 260 kV/cm, reducing significantly the length of the hexapole that is required to focus the beam. We demonstrate the focusing of a molecular beam of NO radicals (X 2Π1/2, v = 0, J = 1/2, f) using a hexapole of only 30 cm length. A beamstop is integrated inside the hexapole at the geometric center of the device where the molecular trajectories have the largest deviation from the beam axis, effectively blocking the carrier gas of the molecular beam at minimum loss of NO density. The performance of the hexapole state-selector is investigated by state-selective laser induced fluorescence detection, as well as by two-dimensional imaging of the focused packet of NO radicals. The resulting packet of NO radicals has a density of 9 ± 3 × 1010 cm-3 and a state purity of 99%. [ABSTRACT FROM AUTHOR]