Vacuum Ultraviolet Beamline Research Articles

Photoinduced fragmentation of gas-phase protonated leucine- enkephalin peptide in the VUV range

In this article we report new results for action spectroscopy of protonated peptide Leucine enkephalin (YGGFL). By coupling a linear ion trap mass spectrometer with a vacuum ultraviolet (VUV) synchrotron radiation beamline, we investigate photofragmentation pattern of this peptide, through the analysis of tandem mass spectra recorded over a range of VUV photon energies, below and above the ionization energy. The obtained fragmentation patterns are discussed and compared to previous results.

In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

The ionisation energy of cyclopentadienone: a photoelectron–photoion coincidence study

Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck–Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

Photostimulated phosphor based image plate detection system for HRVUV beamline at Indus-1 synchrotron radiation source

A high resolution vacuum ultraviolet (HRVUV) beamline based on a 6.65m off-plane Eagle spectrometer is in operation at the Indus-1 synchrotron radiation source, RRCAT, Indore, India. To facilitate position sensitive detection and fast spectral recording, a new BaFBr:Eu2+ phosphor based image plate (IP) detection system interchangeable with the existing photomultiplier (PMT) scanning system has been installed on this beamline. VUV photoabsorption studies on Xe, O2, N2O and SO2 are carried out to evaluate the performance of the IP detection system. An FWHM of ~0.5Å is achieved for the Xe atomic line at 1469.6Å. Reproducibility of spectra is found to be within the experimental resolution. Compared to the PMT scanning system, the IP shows several advantages in terms of sensitivity, recording time and S/N ratio, which are highlighted in the paper. This is the first report of incorporation of an IP detection system in a VUV beamline using synchrotron radiation. Commissioning of the new detection system is expected to greatly enhance the utilization of the HRVUV beamline as a number of spectroscopic experiments which require fast recording times combined with a good signal to noise ratio are now feasible.

Flame structure of a low-pressure laminar premixed and lightly sooting acetylene flame and the effect of ethanol addition

The flame structure of a fuel-rich (ϕ=2.4), laminar premixed, and lightly sooting acetylene flame at 40mbar and the influence of ethanol addition on the species pool was investigated. Special emphasis was put on the analysis of important soot precursors like propargyl, benzene, and the polyynes. The mole fractions of more than 50 stable and radical species up to m/z=170 are obtained experimentally in the flames by molecular-beam mass spectrometry (MBMS) in combination with single-photon ionization (SPI) by vacuum ultraviolet (VUV) radiation from the Advanced Light Source (ALS) in Berkeley, CA, USA. For the neat acetylene flame, successful measurements were performed with a combination of MBMS and imaging photoelectron photoion coincidence spectrometry (iPEPICO) at the VUV beamline at the Swiss Light Source (SLS) in Villigen, Switzerland and adding additional species information to the data set. Some interesting isomers (C3H2, C4H5, C4H2O) can be clearly identified by comparison of measured photoionization efficiency (PIE) curves or threshold photoelectron (TPE) spectra with Franck–Condon simulations or literature spectra, respectively. Because of apparatus improvements, the chemical resolution in this study goes beyond prior work and provides a high-quality data set for the development of reaction mechanisms at fuel-rich, low-pressure conditions.

Photochemistry of solid interstellar molecular samples exposed to vacuum-ultraviolet synchrotron radiation

At the vacuum-ultraviolet (VUV) beamline of the Taiwan synchrotron, an end station for photochemistry coupled to instruments to record infrared absorption spectra and ultraviolet and visible emission spectra is used to investigate the photolysis of samples of gases condensed at 3K. This end station is applicable to explore the VUV photochemistry of interstellar molecules in solid samples. For demonstration, we discuss the response of solid dinitrogen to VUV irradiation. In the future, the upgraded photochemistry end station is applicable to investigate the cometary mixed-ice analogs excited with VUV light from the synchrotron.

Vacuum Ultraviolet Action Spectroscopy of Polysaccharides

We studied the optical properties of gas-phase polysaccharides (maltose, maltotetraose, and maltohexaose) ions by action spectroscopy using the coupling between a quadrupole ion trap and a vacuum ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility (France) in the 7 to 18eV range. The spectra provide unique benchmarks for evaluation of theoretical data on electronic transitions of model carbohydrates in the VUV range. The effects of the nature of the charge held by polysaccharide ions on the relaxation processes were also explored. Finally the effect of isomerization of polysaccharides (with melezitose and raffinose) on their photofragmentation with VUV photons is presented.

VUV photochemistry simulation of planetary upper atmosphere using synchrotron radiation

The coupling of a gas reactor, named APSIS, with a vacuum-ultraviolet (VUV) beamline at the SOLEIL synchrotron radiation facility, for a photochemistry study of gas mixtures, is reported. The reactor may be irradiated windowless with gas pressures up to hundreds of millibar, and thus allows the effect of energetic photons below 100 nm wavelength to be studied on possibly dense media. This set-up is perfectly suited to atmospheric photochemistry investigations, as illustrated by a preliminary report of a simulation of the upper atmospheric photochemistry of Titan, the largest satellite of Saturn. Titan's atmosphere is mainly composed of molecular nitrogen and methane. Solar VUV irradiation with wavelengths no longer than 100 nm on the top of the atmosphere enables the dissociation and ionization of nitrogen, involving a nitrogen chemistry specific to nitrogen-rich upper atmospheres.

DELICIOUS III: A multipurpose double imaging particle coincidence spectrometer for gas phase vacuum ultraviolet photodynamics studies

We present a versatile double imaging particle coincidence spectrometer operating in fully continuous mode, named DELICIOUS III, which combines a velocity map imaging device and a modified Wiley-McLaren time of flight momentum imaging analyzer for photoelectrons and photoions, respectively. The spectrometer is installed in a permanent endstation on the DESIRS vacuum ultraviolet (VUV) beamline at the French National Synchrotron Radiation Facility SOLEIL, and is dedicated to gas phase VUV spectroscopy, photoionization, and molecular dynamics studies. DELICIOUS III is capable of recording mass-selected threshold photoelectron photoion coincidence spectra with a sub-meV resolution, and the addition of a magnifying lens inside the electron drift tube provides a sizeable improvement of the electron threshold/ion mass resolution compromise. In fast electron mode the ultimate kinetic energy resolution has been measured at ΔE/E = 4%. The ion spectrometer offers a mass resolution--full separation of adjacent masses--of 250 amu for moderate extraction fields and the addition of an electrostatic lens in the second acceleration region allows measuring the full 3D velocity vector for a given mass with an ultimate energy resolution of ΔE/E = 15%, without sacrificing the mass resolution. Hence, photoelectron images are correlated both to the mass and to the ion kinetic energy and recoil direction, to access the electron spectroscopy of size-selected species, to study the photodissociation processes of state-selected cations in detail, or to measure in certain cases photoelectron angular distributions in the ion recoil frame. The performances of DELICIOUS III are explored through several examples including the photoionization of N2, NO, and CF3.

Performance of PF BL-13A, a vacuum ultraviolet and soft X-ray undulator beamline for studying organic thin films adsorbed on surfaces

We report on the present status of a vacuum ultraviolet and soft X-ray undulator beamline, BL-13A, located at the Photon Factory. BL-13A is mainly dedicated to the study of organic thin films adsorbed on well-defined surfaces, using angle-resolved photoelectron spectroscopy (ARPES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). The photon-energy resolution (E/ΔE) is estimated to be about 10000 at a photon energy of 64 eV with an exit-slit width of 30 μm. The photon intensity is estimated to be 2.9 × 1012 to 5.6 × 108 photons/s for photon energies of 30-1600 eV with an exit-slit width of 100 μm at the ring current of 450 mA. An ultrahigh vacuum (UHV) chamber equipped with an electron-energy analyzer (Gamma Data/Scienta, SES 200) is used as the main end station for ARPES, XPS, and XAS measurements. A sample can be transferred from a UHV chamber for sample preparation or from a UHV chamber for the evaporation of organic materials. The sample-holder acceptors are equipped with a heating and cooling system. The overall electron-energy resolution is estimated to be about 12 meV at a photon energy of 30 eV.

Monochromator operation in the carbon window region at the reflectometry beamline BL-11D of the Photon Factory

The vacuum ultraviolet (VUV) and soft X-ray beamline BL-11D of the Photon Factory has been recently equipped with a reflectometer to be dedicated to reflectometry for optical elements. The monochromator is of a varied deviation angle type. Focus conditions had been achieved using photoelectron spectroscopy data in the separated regions of 60–200 eV and 300–700 eV with respective gratings. Relying on the monochromator parameters, we programmed a monochromator operation optimized to 250-300 eV region for characterization of carbon window multilayers. Spectral reflectance of a Cr/C multilayer was measured at various angles of incidence, and the peak energy changed, showing that the monochromator has a good spectral accuracy as well as a high resolving power. We also programmed a monochromator operation above 700 eV, and the operable energy range has been extended to 200–1000 eV with one grating. The spectral transmittance and reflectances of Co/C multilayers were measured, and the spectral impurities were discussed.

A soft x-ray transmission grating imaging-spectrometer for the National Ignition Facility

A soft x-ray transmission grating spectrometer has been designed for use on high energy-density physics experiments at the National Ignition Facility (NIF); coupled to one of the NIF gated x-ray detectors it records 16 time-gated spectra between 250 and 1000 eV with 100 ps temporal resolution. The trade-off between spectral and spatial resolution leads to an optimized design for measurement of emission around the peak of a 100-300 eV blackbody spectrum. Performance qualification results from the NIF, the Trident Laser Facility and vacuum ultraviolet beamline at the National Synchrotron Light Source, evidence a <100 μm spatial resolution in combination with a source-size limited spectral resolution that is <10 eV at photon energies of 300 eV.

A new double imaging velocity focusing coincidence experiment: i2PEPICO

The vacuum ultraviolet (VUV) beamline of the Swiss Light Source has been upgraded after two years of operation. A new, turntable-type monochromator was constructed at the Paul Scherrer Institut, which allows for fast yaw-alignment as well as quick grating change and exchange. In addition to the original imaging photoelectron photoion coincidence endstation (iPEPICO), a second, complementary double imaging setup (i(2)PEPICO) has been built. Volatile samples can be introduced at room temperature or in a molecular beam, a pyrolysis source allows for radical production, and non-volatile solids can be evaporated in a heated cell. Monochromatic VUV radiation ionizes the sample and both photoelectrons and photoions are velocity map imaged onto two fast position sensitive detectors and detected in delayed coincidence. High intensity synchrotron radiation leads to ionization rates above 10(5) s(-1). New data acquisition and processing approaches are discussed for recording coincidence processes at high rates. The setup is capable of resolving pulsed molecular beam profiles and the synchrotron time structure temporally. The latter is shown by photoelectron autocorrelation, which displays both the 1.04 MHz ring clock frequency as well as resolving the micro-pulses with a separation of 2 ns. Kinetic energy release analysis on the dissociative photoionization of CF(4) indicates a dissociation mechanism change in the Franck-Condon allowed energy range of the first ion state.

In situremoval of carbon contamination from optics in a vacuum ultraviolet and soft X-ray undulator beamline using oxygen activated by zeroth-order synchrotron radiation

Carbon contamination of optics is a serious issue in all soft X-ray beamlines because it decreases the quality of experimental data, such as near-edge X-ray absorption fine structure, resonant photoemission and resonant soft X-ray emission spectra in the carbon K-edge region. Here an in situ method involving the use of oxygen activated by zeroth-order synchrotron radiation was used to clean the optics in a vacuum ultraviolet and soft X-ray undulator beamline, BL-13A at the Photon Factory in Tsukuba, Japan. The carbon contamination of the optics was removed by exposing them to oxygen at a pressure of 10(-1)-10(-4) Pa for 17-20 h and simultaneously irradiating them with zeroth-order synchrotron radiation. After the cleaning, the decrease in the photon intensity in the carbon K-edge region reduced to 2-5%. The base pressure of the beamline recovered to 10(-7)-10(-8) Pa in one day without baking. The beamline can be used without additional commissioning.

First commissioning results from high resolution vacuum ultraviolet beamline at Indus-1 synchrotron source

A high resolution vacuum ultraviolet beamline has been developed and installed at the 450 MeV synchrotron source Indus-1 operating at the Raja Ramanna Centre for Advance Technology, Indore, India. This beamline is useful for photoabsorption studies of atoms and molecules in the VUV region of 1050–3000 Å. The beamline consists of three major components: a pre-focusing optical system, a gas phase absorption setup and a 6.65 m vacuum ultraviolet spectrometer in off-plane Eagle mount. The performance of the beamline has been evaluated by recording VUV absorption spectra of xenon, oxygen and sulphur dioxide using synchrotron radiation from Indus-1. The resolution achieved is 0.1 Å with a 1200 ln/mm grating. Spectra obtained agree well with the ones published earlier. Details of the design, development and performance testing of the beamline are discussed.

Present Status of a New Vacuum Ultraviolet and Soft X-Ray Undulator Beamline BL-13A for the Study of Organic Thin Films Adsorbed on Surfaces

The present status of a new vacuum ultraviolet/soft X-ray (VUV/SX) beamline (BL-13A) used for the study of organic thin films adsorbed on surfaces is described. The base pressure of BL-13A is maintained below 1×10−8 Pa in order to prevent contamination of the optics by residual gases. The measured performance is as follows: photon-energy region, 30-1,200 eV; photon flux, 109-1011 photons s−1; photon-energy resolution (E/ΔE), 10,000 at a photon energy of 401 eV; spot size (horizontal\ imes;vertical) at the second focus, ≈630×120 μm; photon-energy drift, ≤±0.02 eV at a photon energy of 244.39 eV; reduction of photon flux in the C K-edge region, ∼50%.

Three grating monochromator for the vacuum-ultraviolet radiation beamline at the Swiss Light Source

The beamline optics of the vacuum-ultraviolet radiation beamline installed on a bending magnet of the Swiss Light Source are to be upgraded. Supports for all three optical elements of the beamline optics (collimating mirror, plane grating monochromator and focusing mirror) have been re-designed to allow a more stable and improved fine tuning. The monochromator is composed of a set of three interchangeable gratings mounted on a rotatable platform. Each grating is framed in an optimized goniometer mount, designed and built in-house, which uses flexible elements for precise and reproducible adjustments. The roll and yaw of the gratings can be adjusted with microradian precision to minimize conical diffraction.

Heats of Vaporization of Room Temperature Ionic Liquids by Tunable Vacuum Ultraviolet Photoionization

The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be DeltaH(vap)(298.15 K) = 195 +/- 19 kJ mol(-1). The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (DeltaH(vap)(298.15 K) = 174 +/- 12 kJ mol(-1)) and N-butyl-N-methylpyrrolidinium dicyanamide (DeltaH(vap)(298.15 K) = 171 +/- 12 kJ mol(-1)) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion pairs.

Pre-flight calibration of LYRA, the solar VUV radiometer on board PROBA2

<i>Aims. <i/>LYRA, the Large Yield Radiometer, is a vacuum ultraviolet (VUV) solar radiometer, planned to be launched in November 2009 on the European Space Agency PROBA2, the Project for On-Board Autonomy spacecraft.<i>Methods. <i/>The instrument was radiometrically calibrated in the radiometry laboratory of the Physikalisch-Technische Bundesanstalt (PTB) at the Berlin Electron Storage ring for SYnchroton radiation (BESSY II). The calibration was done using monochromatized synchrotron radiation at PTB's VUV and soft X-ray radiometry beamlines using reference detectors calibrated with the help of an electrical substitution radiometer as the primary detector standard.<i>Results. <i/>A total relative uncertainty of the radiometric calibration of the LYRA instrument between 1% and 11% was achieved. LYRA will provide irradiance data of the Sun in four UV passbands and with high temporal resolution down to 10 ms. The present state of the LYRA pre-flight calibration is presented as well as the expected instrument performance.

Vacuum ultraviolet beamline at the Swiss Light Source for chemical dynamics studies

A bend-magnet vacuum ultraviolet (VUV) beamline, intended for chemical dynamics studies, was constructed and brought into operation at the Swiss Light Source (SLS) of the Paul Scherrer Institut. The beamline delivers synchrotron radiation in the 5–30 eV photon energy range with a photon flux of 10 11 photons/s at 10 eV and 10 12 photons/s at 20 eV with a resolving power of 2500. The resolving power increases to 10 4 at the cost of photon flux. An in-house designed rare gas filter is used to suppress higher harmonic radiation by a factor of >10 4, yielding purely monochromatic light in the energy range of 5–21.6 eV. The filter is compact, easy to align, requires a total pumping power of less than 645 l/s and consumes only 3 normal l/h of filter gas. It is located at the end of the beamline, right in front of the experimental endstation. It is usually operated at a higher pressure than the endstation, which offers the additional benefit of protecting the beamline vacuum from sample contamination.