DESIRS is a new undulator-based VUV beamline on the 2.75 GeV storage ring SOLEIL (France) optimized for gas-phase studies of molecular and electronic structures, reactivity and polarization-dependent photodynamics on model or actual systems encountered in the universe, atmosphere and biosphere. It is equipped with two dedicated endstations: a VUV Fourier-transform spectrometer (FTS) for ultra-high-resolution absorption spectroscopy (resolving power up to 10(6)) and an electron/ion imaging coincidence spectrometer. The photon characteristics necessary to fulfill its scientific mission are: high flux in the 5-40 eV range, high spectral purity, high resolution, and variable and well calibrated polarizations. The photon source is a 10 m-long pure electromagnetic variable-polarization undulator producing light from the very near UV up to 40 eV on the fundamental emission with tailored elliptical polarization allowing fully calibrated quasi-perfect horizontal, vertical and circular polarizations, as measured with an in situ VUV polarimeter with absolute polarization rates close to unity, to be obtained at the sample location. The optical design includes a beam waist allowing the implementation of a gas filter to suppress the undulator high harmonics. This harmonic-free radiation can be steered toward the FTS for absorption experiments, or go through a highly efficient pre-focusing optical system, based on a toroidal mirror and a reflective corrector plate similar to a Schmidt plate. The synchrotron radiation then enters a 6.65 m Eagle off-plane normal-incidence monochromator equipped with four gratings with different groove densities, from 200 to 4300 lines mm(-1), allowing the flux-to-resolution trade-off to be smoothly adjusted. The measured ultimate instrumental resolving powers are 124000 (174 µeV) around 21 eV and 250000 (54 µeV) around 13 eV, while the typical measured flux is in the 10(10)-10(11) photons s(-1) range in a 1/50000 bandwidth, and 10(12)-10(13) photons s(-1) in a 1/1000 bandwidth, which is very satisfactory although slightly below optical simulations. All of these features make DESIRS a state-of-the-art VUV beamline for spectroscopy and dichroism open to a broad scientific community.

We report here the recent upgrade of the SAPHIRS permanent photoionization end-station at the DESIRS vacuum ultraviolet beamline of synchrotron SOLEIL, whose performances have been enhanced by installing an additional double-skimmer differential chamber. The smaller molecular beam profile obtained at the interaction region has increased the mass resolution of the double imaging photoelectron photoion coincidence (i(2)PEPICO) spectrometer, DELICIOUS III, installed in the photoionization chamber of the SAPHIRS endstation, by a factor of two, to M/ΔM ∼ 1700 (FWHM). The electron kinetic energy resolution offered by the velocity map imaging (VMI) part of the spectrometer has been improved down to 2.8% (ΔE/E) as we show on the N2 photoionization case in the double skimmer configuration. As a representative example of the overall state-of-the-art i(2)PEPICO performances, experimental results of the dissociation of state-selected O2(+)(B(2)∑(g)(-), v(+) = 0-6) molecular ions performed at the fixed photon energy of hν = 21.1 eV are presented.

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A novel experimental technique for tandem mass spectrometry and ion spectroscopy of electrosprayed ions using vacuum-ultraviolet (VUV) synchrotron radiation is presented. Photon activation of trapped precursor ions has been performed by coupling a commercial linear quadrupole ion trap (Thermo scientific LTQ XL), equipped with the electrosprayed ions source, to the DESIRS beamline at the SOLEIL synchrotron radiation facility. The obtained results include, for the first time on biopolymers, photodetachment spectroscopy using monochromated synchrotron radiation of multi-charged anions and the single photon ionization of large charge-selected polycations. The high efficiency and signal-to-noise ratio achieved by the present set-up open up possibilities of using synchrotron light as a new controllable activation method in tandem mass spectrometry of biopolymers and VUV-photon spectroscopy of large biological ions.

We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X(3)Σ(-) ground state of the OH(+) and OD(+) cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.