Laser-based ion source for mass spectrometry and laser spectroscopy of negative ions

Boesl, U.; Bäßmann, C.; Drechsler, Gerhard; Distelrath, Volker

doi:10.1255/ejms.309

Cited by 15 publications

(11 citation statements)

References 58 publications

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“…1 Several detachment studies of this species have probed the photon energy dependence of the total detachment cross section [19][20][21][22][23][24][25][26] or reported the photoelectron spectrum of O 2 − . 1,[27][28][29][30][31][32][33][34][35][36][37][38] Until very recently, much less data were reported regarding the PAD. 1,28,35 Among other anions, the prominent dependence of photoelectron anisotropy on the final vibrational state of the neutral was reported in the photodetachment of NO − .…”

Section: Introductionmentioning

confidence: 99%

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

Duzor

Mbaiwa

Wei

et al. 2010

The Journal of Chemical Physics

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The ZCC model invokes vibrational channel specific "detachment orbitals" and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O 2 : the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.

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Section: Introductionmentioning

confidence: 99%

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

Duzor

Mbaiwa

Wei

et al. 2010

The Journal of Chemical Physics

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“…The authors are aware of only one other recent report on the use of photoelectron attachment as an ionization mechanism for mass spectrometry [17]. Boesl et al [17] proposed a fixed wavelength, laser-based photoelectron emission source combined with supersonic beam expansion and provided examples for its application to mass spectral analysis.…”

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confidence: 99%

“…Boesl et al [17] proposed a fixed wavelength, laser-based photoelectron emission source combined with supersonic beam expansion and provided examples for its application to mass spectral analysis. The present work is intended to further evaluate the utility of low energy photoelectrons as a soft ionization source for mass spectrometry.…”

mentioning

confidence: 99%

Photoelectron resonance capture ionization (PERCI): A novel technique for the soft-ionization of organic compounds

LaFranchi

Petrucci

2004

J. Am. Soc. Mass Spectrom.

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Photoelectron resonance capture ionization (PERCI) is demonstrated as a sensitive ionization technique involving minimal fragmentation of organic molecules. PERCI has been used successfully to softly and efficiently ionize both strongly UV absorbing and non-absorbing molecules. Tunable low energy (Ͻ1 eV) electrons are generated by focusing a pulsed UV laser on an aluminum photocathode in the presence of gas phase analyte. Negative ions are formed through a resonance electron capture process. Mass analysis is done using a reflectron time-of-flight mass spectrometer. PERCI is demonstrated for a number of gas phase compounds and simple mixtures, including sulfur hexafluoride, nitrobenzene, nitrophenol, 2-pentanone, hexanal, heptanal, and octanal. In all cases the molecular ion (or [M Ϫ H] Ϫ ) was observed to be the dominant peak. The 1 limit of detection was estimated to be on the order of 10 6 molecules in the ionization region. . It has been shown that the result of low energy electron attachment depends heavily upon the electron energy [1]. For instance, at a particular electron energy ( ), associative attachment can occur leaving the molecular anion radical present. At a different , dissociative electron attachment can occur in which the molecule breaks apart to give a neutral radical species and a fragment anion. The favored pathway is also a function of the structural and electronic properties of the molecule. The electron capture phenomenon, known as resonance electron capture (REC), has proved to be a very useful ionization method for the detection of a variety of classes of organic compounds by mass spectrometry. It has been shown to efficiently ionize organic molecules functionalized with halogens, nitrates, sulfur, conjugated -systems and carbonyls [2][3][4][5], as well as straight-chain hydrocarbons with minimal functionality [6]. Most recently, the versatility of REC ionization was underlined in the literature for chromatographic detection [7].As an example of REC, the reactions at two different electron capture resonances (associative and dissociative) of nitrobenzene are shown below [8].In Reaction 1, capture of zero energy electrons is an efficient process for producing intact molecular ions. In addition, through Reaction 2, higher electron energy resonances are also available for electron capture producing the NO 2 Ϫ fragment. These higher energy resonances can improve the analytical selectivity of REC in the case of compound mixtures.Two instruments capable of REC ionization, suited for gas phase studies, are the throchoidal electron monochromator [9] and the reversal electron attachment detector (READ) [10]. The electron monochromator uses crossed electric and magnetic fields to force different trajectories on electrons with different energies. An offset exit aperture allows monoenergetic electrons to pass into the source region of a mass spectrometer. A more detailed discussion can be found in the reference by Laramee et al. [9]. READ operates by

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“…Generally, typical anion source used in anionic photoelectron spectroscopy includes laser ablation source, pulsed arc cluster ion source (PAICS), magnetron sputtering source, electrospray ionization source (ESI), electron bombardment ionization source (EI) (electron energy>100 eV). While the anion source based on pulsed UV laser-induced electron attachment (LIEA) to molecule is rarely reported in this field except Boesl et al [12]. In this way, UV laser (355 or 266 nm) is employed to irradiate metal target to produce lowenergy photoelectrons.…”

Section: Introductionmentioning

confidence: 99%

Design Near-threshold Photoelectron Imaging Spectrometer Based on UV Laser Induced Photoelectron Emission Anion Source

Qin

Tang

2013

Chinese Journal of Chemical Physics

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We have developed a compact photoelectron imaging facility, including an anion source with dissociative photoelectron attachment to molecules, a linear time-of-flight mass spectrometry (TOFMS), and an orthogonal high-resolution threshold photoelectron velocity map imaging spectrometer (VMI). Intense and cold cluster anions were prepared in photoelectronattachment processes upon pulsed UV laser ablation of metal target. Combining this anion source with TOFMS-VMI, the achieved mass resolution is about 200, and the electron kinetic energy resolution is better than 3%, i.e., 30 meV for 1 eV electrons. More importantly, low-energy photoelectron imaging spectra for CH 3 S − and S 2 − at 611.46 nm are obtained. In both cases, the refined electron affinities are determined to be 1.8626±0.0020 eV for CH 3 S and 1.6744±0.0035 eV for S 2 , respectively. Preliminary results suggest that the apparatus is a powerful tool for estimating precise electron affinities values from threshold photoelectron imaging spectroscopy.

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Laser-based ion source for mass spectrometry and laser spectroscopy of negative ions

Cited by 15 publications

References 58 publications

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

Photoelectron resonance capture ionization (PERCI): A novel technique for the soft-ionization of organic compounds

Design Near-threshold Photoelectron Imaging Spectrometer Based on UV Laser Induced Photoelectron Emission Anion Source

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