Molecular Ion Beams Research Articles

Simultaneous determination of non-natural isotopic composition of Li and B employing Li2BO2+ by Thermal Ionisation Mass Spectrometry

Abstract Simultaneous isotopic analysis of lithium and boron was carried by Thermal Ionisation Mass Spectrometry employing Li 2 BO 2 + as monitoring ions. This molecular ion beam method (MIBM) requires judicious selection of monitor pairs for the accurate determination of the isotopic ratios. Relative Uncertainty Magnification Factors for Li and B were theoretically evaluated for the simultaneous determination of isotopic abundance ratios of Li and B using Li 2 BO 2 + . The combinations of two molecular ion pairs that can be used for the simultaneous determination of both Li and B when the isotopic abundances of Li or B are different from that of natural abundance were identified based on these theoretical evaluations. It is observed that the selection of the monitor pairs for the simultaneous determination of isotopic composition of lithium and boron is simple when the difference in the isotopic abundance between the atom percent of 6 Li & 10 B is large. The outcome of the theoretical calculations was verified by using the mixtures of lithium and boron with an atom ratio of B/Li about 5 prepared by mixing Svec lithium (a natural isotopic standard of lithium) with the synthetic mixtures of B having 10 B varying from 10% to 95%.

The cryogenic storage ring CSR.

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm(-3) is derived, equivalent to a room-temperature pressure below 10(-14) mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

Production of lanthanide molecular ion beams by fluorination technique

Systematic off-line fluorination studies on all the stable lanthanide isotopes have been performed. The results are presented as a function of various parameters such as the target temperature, the type of ion source used (hot plasma or surface ionization) and the quantity of CF4 introduced. The first on-line measurements allowed us to determine the optimal experimental conditions for producing radioactive lanthanide isotopes.

Mass Spectrometry as a Preparative Tool for the Surface Science of Large Molecules.

Measuring and understanding the complexity that arises when nanostructures interact with their environment are one of the major current challenges of nanoscale science and technology. High-resolution microscopy methods such as scanning probe microscopy have the capacity to investigate nanoscale systems with ultimate precision, for which, however, atomic scale precise preparation methods of surface science are a necessity. Preparative mass spectrometry (pMS), defined as the controlled deposition of m/z filtered ion beams, with soft ionization sources links the world of large, biological molecules and surface science, enabling atomic scale chemical control of molecular deposition in ultrahigh vacuum (UHV). Here we explore the application of high-resolution scanning probe microscopy and spectroscopy to the characterization of structure and properties of large molecules. We introduce the fundamental principles of the combined experiments electrospray ion beam deposition and scanning tunneling microscopy. Examples for the deposition and investigation of single particles, for layer and film growth, and for the investigation of electronic properties of individual nonvolatile molecules show that state-of-the-art pMS technology provides a platform analog to thermal evaporation in conventional molecular beam epitaxy. Additionally, it offers additional, unique features due to the use of charged polyatomic particles. This new field is an enormous sandbox for novel molecular materials research and demands the development of advanced molecular ion beam technology.

Photodissociation of an Internally Cold Beam of CH^{+} Ions in a Cryogenic Storage Ring.

We have studied the photodissociation of CH^{+} in the Cryogenic Storage Ring at ambient temperatures below 10K. Owing to the extremely high vacuum of the cryogenic environment, we were able to store CH^{+} beams with a kinetic energy of ∼60 keV for several minutes. Using a pulsed laser, we observed Feshbach-type near-threshold photodissociation resonances for the rotational levels J=0-2 of CH^{+}, exclusively. In comparison to updated, state-of-the-art calculations, we find excellent agreement in the relative intensities of the resonances for a given J, and we can extract time-dependent level populations. Thus, we can monitor the spontaneous relaxation of CH^{+} to its lowest rotational states and demonstrate the preparation of an internally cold beam of molecular ions.

Sputtering of silicon and glass substrates with polyatomic molecular ion beams generated from ionic liquids

The effect of irradiating 1-ethyl-3-methylimidazolium positive (EMIM+) or dicyanamide negative (DCA–) ion beams using an ionic liquid ion source was characterized concerning its sputtering properties for single crystalline Si(100) and nonalkaline borosilicate glass substrates. The irradiation of the DCA– ion beam onto the Si substrate at an acceleration voltage of 4 and 6 kV exhibited detectable sputtered depths greater than a couple of nanometers with an ion fluence of only 1 × 1015 ions/cm2, while the EMIM+ ion beam produced the same depths with an ion fluence 5 × 1015 ions/cm2. The irradiation of a 4 kV DCA– ion beam at a fluence of 1 × 1016 ions/cm2 also yields large etching depths in Si substrates, corresponding to a sputtering yield of Si/DCA– = 10, and exhibits a smoothed surface roughness of 0.05 nm. The interaction between DCA– and Si likely causes a chemical reaction that relates to the high sputtering yield and forms an amorphous C-N capping layer that results in the smooth surface. Moreover, s...

Production of high current proton beams using complex H-rich molecules at GSI.

In this contribution, the concept of production of intense proton beams using molecular heavy ion beams from an ion source is described, as well as the indisputable advantages of this technique for operation of the GSI linear accelerator. The results of experimental investigations, including mass-spectra analysis and beam emittance measurements, with different ion beams (CH3(+),C2H4(+),C3H7(+)) using various gaseous and liquid substances (methane, ethane, propane, isobutane, and iodoethane) at the ion source are summarized. Further steps to improve the ion source and injector performance with molecular beams are depicted.

Andromede project: Surface analysis and modification with probes from hydrogen to nano-particles in the MeV energy range

The Andromede project is the center of a multi-disciplinary team which will build a new instrument for surface modification and analysis using the impact of probes from hydrogen to nano-particles (Au400+4) in the MeV range. For this new instrument a series of atomic, polyatomic, molecular and nano-particle ion beams will be delivered using two ion sources in tandem, a liquid metal ion source and an electron cyclotron resonance source. The delivered ion beams will be accelerated to high energy with a 4 MeV van de Graaff type accelerator. By using a suite of probes in the MeV energy range, ion beam analysis techniques, MeV atomic and cluster secondary ion mass spectrometry can all be performed in one location. A key feature of the instrument is its ability to produce an intense beam for injection into the accelerator. The commissioning of the two sources shows that intense beams from atomic ions to nano-particles can be delivered for subsequent acceleration. The calculations and measurements for the two sources are presented.

The cryogenic storage ring CSR for collision experiments with state-controlled and phase-space cooled molecular ion beams

SynopsisThe cryogenic storage ring (CSR) for positive and negative atomic, molecular and cluster ions is starting operation at the Max Planck Institute for Nuclear Physics in Heidelberg.

Ion field-evaporation from ionic liquids infusing carbon xerogel microtips

Ionic liquid ion sources capable of producing positive and negative molecular ion beams from room-temperature molten salts have applications in diverse fields, from materials science to space propulsion. The electrostatic stressing of these ionic liquids places the liquid surfaces in a delicate balance that could yield unwanted droplet emission when not properly controlled. Micro-tip emitter configurations are required to guarantee that these sources will operate in a pure ionic regime with no additional droplets. Porous carbon based on resorcinol-formaldehyde xerogels is introduced as an emitter substrate. It is demonstrated that this material can be shaped to the required micron-sized geometry and has appropriate transport properties to favor pure ionic emission. Time-of-flight mass spectrometry is used to verify that charged particle beams contain solvated ions exclusively.

REACTION STUDIES OF NEUTRAL ATOMIC C WITH ${{\rm{H}}}_{3}^{+}$ USING A MERGED-BEAMS APPARATUS

We have investigated the chemistry of ${\rm C + H_3^+}$ forming CH$^+$, CH$_2^+$, and CH$_3^+$. These reactions are believed to be some of the key gas-phase astrochemical processes initiating the formation of organic molecules in molecular clouds. For this work we have constructed a novel merged fast-beams apparatus which overlaps a beam of molecular ions onto a beam of ground-term neutral atoms. Here we present cross section data for forming CH$^+$ and CH$_2^+$ at collision energies from $\approx 9$ meV to $\approx20$ and 3 eV, respectively. Using these data we have derived thermal rate coefficients for reaction temperatures from $\approx72$ K to $\approx2.3 \times 10^5$ and $3.4 \times 10^4$ K, respectively. For the formation of CH$_3^+$ we are able only to put an upper limit on the rate coefficient. Our results for CH$^+$ and CH$_2^+$ are in good agreement with the mass-scaled results from a previous ion trap study of ${\rm C + D_3^+}$ at a reaction temperature of $\sim 1000$ K. At molecular cloud temperatures our thermal rate coefficient for forming CH$^+$ lies a factor of $\sim 2-4$ below the Langevin rate coefficient currently given in astrochemical databases and below the published semi-classical calculations. Our results for CH$_2^+$ formation are a factor of $\sim 26$ above the semi-classical results. Astrochemical databases do not currently include this channel.

1-, 2- and 3-Pentanol combustion in laminar hydrogen flames – A comparative experimental and modeling study

Oxidation pathways of three different pentanol isomers 1-, 2- and 3-pentanol are investigated using the electron–ionization molecular-beam mass spectrometry (EI-MBMS) technique. New experimental speciation data was obtained from laminar, flat, low-pressure H2/O2/Ar base flames seeded with equal amounts of pre-vaporized 1-, 2- or 3-pentanol. The experimental investigation is supported by kinetic modeling. Here, one single detailed reaction mechanism for the three linear pentanol isomers has been constructed and compared against new and existing experimental data. The model itself was obtained by an open-source reaction model generation software (RMG) and tested against existing ignition delay times, flame speeds and new quantitative experimental results for mole fraction profiles of major and intermediate species. The overall discussion of individual species profiles is guided by the model-based reaction flow analysis focusing on the initial steps of the fuel destruction paths for the three pentanols down to C3-hydrocarbon species. Therefore, the reaction pathways for the initial fuel destruction steps are shown and analyzed using combined experimental and predicted results. Analysis is performed by means of secondary decay products for each of the three pentanols. The kinetic reaction model was successfully tested against available ignition delay time and laminar flame speed data. Comparisons against 23 new quantitative species profiles are presented for each of the pentanol doped flames. In general, a good predictive capability of the detailed model can be noted for all three investigated straight-chain pentanols regarding the mole fraction profiles of major and intermediate species.

Technological developments for strontium-90 determination using AMS

Abstract Accelerator mass spectrometry (AMS) is one of method used for 90 Sr determination. It would enable rapid 90 Sr measurements from environmental samples such as water, soil, and milk. However, routine analysis of 90 Sr using AMS has not yet been achieved because of difficulties associated with isobaric separation and production of intense negative ion beams characterized by currents from hundreds of nanoamperes to several microamperes. We have developed a rapid procedure for preparing samples with optimum compositions for use with AMS, which enables production of intense Sr beam currents from an ion source. Samples of SrF 2 were prepared from a standard Sr solution and agricultural soil. The time required to prepare a SrF 2 sample from a soil sample was 10 h. Negative 88 SrF 3 − ions were successfully extracted at 500 nA from mixed samples of SrF 2 and PbF 2 . In the present work, negative ions of 90 Zr, included as an impurity, were accelerated with a tandem accelerator operated at a terminal voltage of 5 MV. Ions characterized by a charge state of 6+ were channeled into a gas counter. An atomic ratio of 90 Zr/ 88 Sr of 3 × 10 −8 was estimated for the soil sample. No signal was detected from the assay of PbF 2 , which was pressed in an aluminum cathode, for a mass number of 90. PbF 2 revealed good performance in the production of negative SrF 3 − molecular ion beams and detection of 90 Sr with a gas counter.

Active conformation control of unfolded proteins by hyperthermal collision with a metal surface.

The physical and chemical properties of macromolecules like proteins are strongly dependent on their conformation. The degrees of freedom of their chemical bonds generate a huge conformational space, of which, however, only a small fraction is accessible in thermal equilibrium. Here we show that soft-landing electrospray ion beam deposition (ES-IBD) of unfolded proteins allows to control their conformation. The dynamics and result of the deposition process can be actively steered by selecting the molecular ion beam's charge state or tuning the incident energy. Using these parameters, protein conformations ranging from fully extended to completely compact can be prepared selectively on a surface, as evidenced on the subnanometer/amino acid resolution level by scanning tunneling microscopy (STM). Supported by molecular dynamics (MD) simulations, our results demonstrate that the final conformation on the surface is reached through a mechanical deformation during the hyperthermal ion surface collision. Our experimental results independently confirm the findings of ion mobility spectrometry (IMS) studies of protein gas phase conformations. Moreover, we establish a new route for the processing of macromolecular materials, with the potential to reach conformations that would be inaccessible otherwise.

Electron emission fromH2+in strong laser fields

We present an experimental investigation into the angular and energy distributions of electrons set free by the interaction of hydrogen molecular ions with strong laser fields. The results extend on those presented previously [M. Odenweller et al., Phys. Rev. Lett. 107, 143004 (2011)] for circularly polarized light. Pulses of laser light ($\ensuremath{\lambda}=780$ nm, $I\ensuremath{\approx}6\ifmmode\times\else\texttimes\fi{}{10}^{14}$ W cm${}^{\ensuremath{-}2}$, $\ensuremath{\tau}\ensuremath{\approx}40$ fs) of both linear and circular polarization are focused onto an H${}_{2}$${}^{+}$ molecular ion beam. The momenta of the proton and electron fragments are determined in a coincidence experiment, enabling electron momentum emission patterns in the molecular frame to be deduced for specific values of internuclear distances.

Gas feeding molecular phosphorous ion source for semiconductor implanters

Phosphorus is a much used dopant in semiconductor technology. Its vapors represent a rather stable tetratomic molecular compound and are produced from one of the most thermodynamically stable allotropic forms of phosphorus-red phosphorus. At vacuum heating temperatures ranging from 325 °C, red phosphorus evaporates solely as P4 molecules (P4/P2 ∼ 2 × 10(5), P4/P ∼ 10(21)). It is for this reason that red phosphorus is best suited as a source of polyatomic molecular ion beams. The paper reports on experimental research in the generation of polyatomic phosphorus ion beams with an alternative P vapor source for which a gaseous compound of phosphorus with hydrogen - phosphine - is used. The ion source is equipped with a specially designed dissociator in which phosphine heated to temperatures close to 700 °C decomposes into molecular hydrogen and phosphorus (P4) and then the reaction products are delivered through a vapor line to the discharge chamber. Experimental data are presented reflecting the influence of the discharge parameters and temperature of the dissociator heater on the mass-charge state of the ion beam.

Carrier-Envelope Phase Control over Pathway Interference in Strong-Field Dissociation ofH2+

The dissociation of an H2+ molecular-ion beam by linearly polarized, carrier-envelope-phase-tagged 5 fs pulses at 4×10(14) W/cm2 with a central wavelength of 730 nm was studied using a coincidence 3D momentum imaging technique. Carrier-envelope-phase-dependent asymmetries in the emission direction of H+ fragments relative to the laser polarization were observed. These asymmetries are caused by interference of odd and even photon number pathways, where net zero-photon and one-photon interference predominantly contributes at H+ + H kinetic energy releases of 0.2-0.45 eV, and net two-photon and one-photon interference contributes at 1.65-1.9 eV. These measurements of the benchmark H2+ molecule offer the distinct advantage that they can be quantitatively compared with ab initio theory to confirm our understanding of strong-field coherent control via the carrier-envelope phase.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part I: Furan

Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the predominant furan consumption pathway is initiated by H-addition on the carbon atom neighboring the O-atom with acetylene as one of the dominant products.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part III: 2,5-Dimethylfuran

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part II: 2-Methylfuran

This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed.