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Here, we describe our pulsed helium droplet apparatus for spectroscopy of molecular ions. Our approach involves the doping of the droplets of about 10 nm in diameter with precursor molecules, such as ethylene, followed by electron impact ionization. Droplets containing ions are irradiated by the pulsed infrared laser beam. Vibrational excitation of the embedded cations leads to the evaporation of the helium atoms in the droplets and the release of the free ions, which are detected by the quadrupole mass spectrometer. In this work, we upgraded the experimental setup by introducing an octupole RF collision cell downstream from the electron impact ionizer. The implementation of the RF ion guide increases the transmission efficiency of the ions. Filling the collision cell with additional He gas leads to a decrease in the droplet size, enhancing sensitivity to the laser excitation. We show that the spectroscopic signal depends linearly on the laser pulse energy, and the number of ions generated per laser pulse is about 100 times greater than in our previous experiments. These improvements facilitate faster and more reproducible measurements of the spectra, yielding a handy laboratory technique for the spectroscopic study of diverse molecular ions and ionic clusters at low temperature (0.4 K) in He droplets.
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Tandem mass spectrometry using continuous‐wave infrared multiphoton dissociation in an electrostatic linear ion trap
RationaleThe electrostatic linear ion trap (ELIT) can be operated as a multi‐reflection time‐of‐flight (MR‐TOF) or Fourier transform (FT) mass analyzer. It has been shown to be capable of performing high‐resolution mass analysis and high‐resolution ion isolations. Although it has been used in charge‐detection mass spectrometry (CDMS), it has not been widely used as a conventional mass spectrometer for ensemble measurements of ions, or for tandem mass spectrometer. The advantages of tandem mass spectrometer with high‐resolution ion isolations in the ELIT have thus not been fully exploited. MethodsA homebuilt ELIT was modified with BaF2viewports to facilitate transmission of a laser beam at the turnaround point of the second ion mirror in the ELIT. Fragmentation that occurs at the turnaround point of these ion mirrors should result in minimal energy partitioning due to the low kinetic energy of ions at these points. The laser was allowed to irradiate ions for a period of many oscillations in the ELIT. ResultsDue to the low energy absorption of gas‐phase ions during each oscillation in the ELIT, fragmentation was found to occur over a range of oscillations in the ELIT generating a homogeneous ion beam. A mirror‐switching pulse is shown to create time‐varying perturbations in this beam that oscillate at the fragment ion characteristic frequencies and generate a time‐domain signal. This was found to recover FT signal for protonated pYGGFL and pSGGFL precursor ions. ConclusionsFragmentation at the turnaround point of an ELIT by continuous‐wave infrared multiphoton dissociation (cw‐IRMPD) is demonstrated. In cases where laser power absorption is low and fragmentation occurs over many laps, a mirror‐switching pulse may be used to recover varying time‐domain signal. The combination of laser activation at the turnaround points and mirror‐switching isolation allows for tandem MS in the ELIT.
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- Award ID(s):
- 1708338
- PAR ID:
- 10644385
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Rapid Communications in Mass Spectrometry
- Volume:
- 38
- Issue:
- 6
- ISSN:
- 0951-4198
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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