Observation of zwitterion formation in the gas-phase H/D-exchange with CH(3)OD: solution-phase structures in the gas phase.

Infrared spectroscopy of gas-phase singly deuterated [Trp + K](+) (formed by H/D exchange with CH(3)OD) shows that some (approximately 20%) kinetically stable zwitterionic (ZW) conformer is formed, based on the diagnostic antisymmetric CO stretch of the deprotonated carboxylate moiety, upsilon(as)(CO(2)(-)), at 1680 cm(-1). A majority of the deuterated [Trp + K](+) is found to be in the charge solvation (CS) conformation, with deuterium exchange occurring on both the acid and amino groups, which is consistent with H/D scrambling. Interestingly, H/D exchange with the more basic ND(3) reagent did not result in the stabilization of a kinetically stable zwitterion, although it is not clear yet what causes this observation.

IRMPD spectroscopy of metal-ion/tryptophan complexes.

Infrared multiple-photon dissociation (IRMPD) spectroscopy is employed to obtain detailed binding information on singly charged silver and alkali metal-ion/tryptophan complexes in the gas phase. For these complexes the presence of the salt bridge (i.e.

Plasma-surface interaction in the context of ITER.

The decreasing availability of energy and concern about climate change necessitate the development of novel sustainable energy sources. Fusion energy is such a source. Although it will take several decades to develop it into routinely operated power sources, the ultimate potential of fusion energy is very high and badly needed.

Mid-infrared spectroscopy of protected peptides in the gas phase: a probe of the backbone conformation.

Infrared/UV hole-burning spectroscopy is performed on individual conformers of the protected dipeptide Z-Aib-Pro-NHMe. The extended IR range probed in this study allows one to elucidate both the H-bonding motif (5-7 microm) as well as the backbone structure (7-10 microm). Comparison with DFT calculations shows that the backbone is locally constrained to an alpha-conformation by Aib and to a gamma-turn by Pro.

Resonant infrared laser-induced desorption of methane condensed on NaCl(100): isotope mixture experiments.

Resonantly enhanced infrared laser-induced desorption of methane condensed on a single-crystal NaCl(100) surface is observed after excitation with the widely tunable infrared laser output of the free-electron laser at the free-electron laser for infrared experiments facility using mass spectroscopic detection and time-of-flight analysis. Desorption of methane is observed only when the exciting light is in resonance with an internal vibrational mode of the molecule. Different intramolecular modes of the three methane isotopologues under study--CH(4), CD(4), and CD(3)H--are excited; the degenerate deformation mode nu(4) is observed for CH(4) and CD(4) at 7.

Dust transport in a magnetized radio-frequency discharge under microgravity conditions.

Dust is found in plasmas used in industrial applications, such as microelectronics and solar cell manufacturing, in fusion plasmas, where it is usually the result of plasma-wall interactions, and in plasmas in space, such as planetary atmospheres, cometary tails, planetary rings, interstellar molecular clouds, and star and planet formation regions. In plasma applications, magnetic fields are occasionally used, mainly to confine the plasma. In space, however, magnetic fields are very often present and they may strongly influence the behavior of dusty plasma, for instance in the formation of stars and planets.

Vibrational spectroscopy of CO in gas-phase rhodium cluster-CO complexes.

Infrared spectra of isolated unsaturated rhodium cluster-CO complexes in the region of the CO stretching vibration, nu(CO), are measured using a molecular beam depletion technique. These spectra provide benchmarks for interpreting values of nu(CO) that are found when CO is used to probe Rh surfaces and supported Rh nanoparticles. Supported nanoparticles have shifts of nu(CO) of as much as +100 cm-1 compared to the free clusters measured here, indicative of significant charge transfer to the support.

Infrared spectroscopy of gas-phase Cr+ coordination complexes: determination of binding sites and electronic states.

Infrared spectra were recorded for a series of gas-phase Cr+ complexes using infrared multiphoton dissociation (IRMPD) in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The functionalized aromatic ligands (acetophenone, anisole, aniline, and dimethyl aniline) offer a choice of either aromatic ring-pi or n-donor-base binding sites. Use of the FELIX free electron laser light source allowed convenient, rapid scanning of the chemically informative wavelength range from approximately 500 to 1800 cm(-1), which in many cases characterized the preferred site of metal binding, as well as the electronic spin state of the complex.

Charge-state resolved mid-infrared spectroscopy of a gas-phase protein.

Infrared spectra of a 104 amino-acid protein in the gas phase as a function of its charge state are presented. The spectra contain clearly resolvable bands in the amide I and II spectral regions, as well as a band at 1483 cm(-1), which is not observed in solution phase spectroscopy and is especially prominent for the higher charge states. Compared to solution, the amide I band is blue-shifted and the amide II band red-shifted, as expected for species in an environment with reduced hydrogen bonding.

Evidence for high-m secondary islands induced by large low-m islands in a tokamak plasma.

Small-scale structures with high poloidal mode numbers (m=10-20) have been observed in the TEXTOR tokamak plasma with pulsed radar reflectometry and an electron cyclotron emission diagnostic, in conjunction with large 2/1 and 1/1 islands. The small islands have a peaked density profile, similar to that of the simultaneously observed large-scale 2/1 islands. This together with the observation that high-frequency density and temperature fluctuations are very pronounced near the X points of the large islands hints to a strongly perturbed magnetic topology around the X points.

Global plasma turbulence simulations of q = 3 sawtoothlike events in the RTP tokamak.

A two-fluid computer model of electromagnetic tokamak turbulence, CUTIE, is used to study the dynamic structure and turbulent transport in the Rijnhuizen Tokamak Project tokamak. A discharge with dominant, off-axis electron cyclotron heating is the main focus of the simulations which were extended over several resistive diffusion times. CUTIE reproduces the turbulent transport and MHD phenomena of the experiment.

Folding structures of isolated peptides as revealed by gas-phase mid-infrared spectroscopy.

To understand the intrinsic properties of peptides, which are determined by factors such as intramolecular hydrogen bonding, van der Waals bonding and electrostatic interactions, the conformational landscape of isolated protein building blocks in the gas phase was investigated. Here, we present IR-UV double-resonance spectra of jet-cooled, uncapped peptides containing a tryptophan (Trp) UV chromophore in the 1000-2000 cm(-1) spectral range. In the series Trp, Trp-Gly and Trp-Gly-Gly (where Gly stands for glycine), the number of detected conformers was found to decrease from six (Snoek et al.

Vibrational spectroscopy of a non-aromatic amino acid-based model peptide: identification of the gamma-turn motif of the peptide backbone.

The first infrared hole burning spectrum of a gas-phase neutral peptide not containing an aromatic amino acid is presented. In the model peptide Z-Pro-NHMe, the amide I and II bands in the 1500-1800 cm(-1) region appear to be a clear diagnostic for the secondary structure of the backbone, while the analysis of a series of coupled CH bending modes in the 1000-1500 cm(-1) region allows to distinguish between different possible orientations of the chromophore. The geometry of the peptide is strongly constrained by the proline and only one conformation of the backbone is observed, which is identified as a hydrogen bonded gamma-turn.

Gas-phase IR spectroscopy of anionic iron carbonyl clusters.

The first gas-phase vibrational spectra are presented for several anionic iron carbonyl clusters, ranging in size from Fe(CO)4- to Fe5(CO)14- in the CO-stretching region (1600-2100 cm-1). The experimental spectra provide some immediate structural information about the clusters in the form of low-wavenumber (1750-1850 cm-1) bands marking the presence of bridging carbonyl ligands (mu2-COs). Supporting DFT calculations are presented for the smaller clusters (<3 Fe atoms) and give good agreement with the experimental data, allowing structural assignments for these cases.

Electro-optic technique with improved time resolution for real-time, nondestructive, single-shot measurements of femtosecond electron bunch profiles.

Electro-optic detection of the Coulomb field of a relativistic electron bunch combined with single-shot cross correlation of optical pulses is used to enable single-shot measurements of the shape and length of femtosecond electron bunches. This method overcomes a fundamental time-resolution limit of previous single-shot electro-optic measurements, which arises from the inseparability of time and frequency properties of the probing optical pulse. Using this new technique we have made real-time measurements of a 50 MeV electron bunch, observing the profile of 650 fs FWHM ( approximately 275 fs rms) long bunches.

Structure determination of isolated metal clusters via far-infrared spectroscopy.

We present a new method for the size selective structure determination of small isolated metal clusters in the gas phase. The technique is applied to cationic vanadium clusters containing 6 to 23 atoms, whose far infrared absorption spectra are measured in the 140-450 cm(-1) spectral range. The spectra are unique for each cluster size and are true fingerprints of the cluster's structure.

The site of Cr+ attachment to gas-phase aniline from infrared spectroscopy.

Infrared spectroscopy of gas-phase Cr+ complexes of aniline was studied using the FELIX free electron laser interfaced to a Fourier transform ion cyclotron resonance spectrometer. For both the monomer complex Cr+(aniline) and the dimer complex Cr+(aniline)2 the spectra showed features indicating binding of the metal ion to the aromatic pi cloud, as opposed to the nitrogen atom. Agreement with DFT-calculated infrared absorption spectra for the ring-bound complexes was good using the MPW1PW91 functional, but the B3LYP functional predicted the wrong binding site.

Vortices in dust clouds under microgravity: A simple explanation.

Clouds of dust particles in radio frequency discharges often show a periodic vortexlike motion, especially near the edges of the electrodes or near the tip of an electrostatic probe. These vortices often last as long as the discharge is powered. In a previous paper we have followed a small number of individual dust particles in a discharge under microgravity conditions, moving under the influence of forces computed by means of a self-consistent two-dimensional hydrodynamic model, and interacting via a screened Coulomb potential.

The structures of vanadium oxide cluster-ethene complexes. A combined IR multiple photon dissociation spectroscopy and DFT calculation study.

Infrared spectra of complexes of small vanadium oxide clusters with ethene are determined using infrared multiple photon dissociation (IR-MPD) spectroscopy in the range of 550-1850 cm-1. The structures of the complexes have been identified by comparison of the experimental spectra with the harmonic vibrational frequencies and corresponding IR intensities of possible isomers calculated with DFT methods. We find that the ethene molecule binds directly to a vanadium atom in the cluster, although this it is not in all cases the most stable arrangement.

Infrared spectroscopy of neutral C7H7 isomers: benzyl and tropyl.

The gas-phase infrared absorption spectra of neutral benzyl and tropyl, isomers of formula C7H7, have been measured in the 400-1800 cm-1 spectral region. In addition, a quantum chemical calculation has been performed to model the infrared spectra. For the benzyl radical, the theory shows satisfactory overlap with the experiment, although vibrations involving the CH2 group might be anharmonic.

Infrared spectroscopy of niobium oxide cluster cations in a molecular beam: identifying the cluster structures.

Infrared spectra of niobium oxide cluster cations are measured via IR multiple photon dissociation spectroscopy in the 400-1650 cm(-1) region. The cluster cations are obtained directly from a laser vaporization source and irradiated with the infrared light emitted by a free electron laser. For those oxide clusters that fragment after excitation, the IR spectra are recorded by measuring the cluster intensity changes as a function of the IR wavelength.

Cold molecules.

During the last years there has been a rapidly growing interest in the field of cold molecules. This has obviously been inspired by the spectacular successes in the closely related field of cold atoms, which have recently been recognized by the award of the 2001 Nobel Prize in Physics to Cornell, Ketterle, and Wieman. But molecules have much more to offer than simply extending the experiments already performed with atoms to more complex species.

Long-pulse operation at constant output power and single-frequency mode of a high-power electrostatic free-electron maser with depressed collector.

The Fusion Free-Electron Maser (FFF) is the prototype of a high-power, tunable source of mm-wave radiation, for use on fusion plasma devices. In previous experiments a net output power of 730 kW at 206 GHz was generated in short pulses. The present experiment has been equipped with a system to recover the charge and energy of the spent electron beam.

Structure determination of gas-phase niobium and tantalum carbide nanocrystals via infrared spectroscopy.

Niobium and tantalum carbide clusters have been isolated in the gas phase and irradiated with intense tunable infrared (IR) light. Stable neutral clusters are selectively ionized and subsequently detected in a mass spectrometer. By tuning the IR frequency, infrared multiphoton absorption spectra are obtained for a whole range of clusters.

Alternate gradient focusing and deceleration of a molecular beam.

Neutral dipolar molecules can be decelerated and trapped using time-varying inhomogeneous electric fields. This has been demonstrated only for molecules in low-field seeking states, but can, in principle, be performed on molecules in high-field seeking states as well. Transverse stability is then much more difficult to obtain, however, since molecules in high-field seeking states always experience a force towards the electrodes.