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Updated: Sep 4, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Simultaneous on-line vacuum single- and multi-photon ionization on an orthogonal acceleration time-of-flight mass
J Heide1, S Ehlert1,2, T Koziorowski3
1Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock, Germany. sven.ehlert@photonion.de.
This study introduces a novel system combining single-photon ionization (SPI) and resonance enhanced multi-photon ionization (REMPI) with orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry. This advanced technique enhances analytical capabilities for complex sample analysis, offering richer data and improved efficiency.
Area of Science:
- Analytical Chemistry
- Mass Spectrometry
- Spectroscopy
Background:
- Orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry offers superior mass accuracy and resolving power compared to conventional TOF instruments.
- Continuous ion sources are preferred for high duty cycles, while pulsed sources require high repetition rates for broad mass range coverage.
- Combining different ionization techniques can provide complementary information for comprehensive analysis.
Purpose of the Study:
- To develop and demonstrate a novel system integrating a continuous single-photon ionization (SPI) source and a pulsed resonance enhanced multi-photon ionization (REMPI) source with an oa-TOF mass spectrometer.
- To showcase the simultaneous operation of SPI and REMPI for comprehensive mass spectral analysis without ion storage.
- To evaluate the system's robustness and applicability in real-world industrial environments.
Main Methods:
- A deuterium lamp single-photon ionization (SPI) source was coupled with a pulsed 2000 Hz excimer (KrF) laser for resonance enhanced multi-photon ionization (REMPI).
- The SPI and REMPI sources were integrated with an orthogonal acceleration time-of-flight (oa-TOF) mass spectrometer, enabling simultaneous data acquisition.
- A second data acquisition card was implemented for independent storage of SPI and REMPI data, allowing for targeted analysis and modified sensitivities.
Main Results:
- The combined SPI/REMPI-oa-TOF system successfully acquired complementary data from both ionization methods simultaneously.
- Demonstrated applications included on-line monitoring of coffee roast gas emissions and e-cigarette vapor, as well as gas chromatography (GC) measurements.
- The system exhibited high robustness in industrial settings, providing a higher density of information per measurement and saving time and resources.
Conclusions:
- The developed SPI/REMPI-oa-TOF system represents a significant advancement in mass spectrometry, offering a versatile platform for complex sample analysis.
- The simultaneous use of soft broadband (SPI) and selective soft (REMPI) ionization techniques enables comprehensive mass range coverage and targeted monitoring.
- This robust and efficient system provides valuable complementary information, enhancing analytical capabilities for diverse applications.
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