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Title: Multiplexed characterization of complex gas-phase mixtures combining chirped-pulse Fourier transform microwave spectroscopy and VUV photoionization time-of-flight mass spectrometry

Journal Article · · Review of Scientific Instruments
DOI:https://doi.org/10.1063/1.5046085· OSTI ID:1540250
 [1];  [2];  [2];  [2]; ORCiD logo [2]
  1. Purdue Univ., West Lafayette, IN (United States); Univ. of Rennes 1 (France)
  2. Purdue Univ., West Lafayette, IN (United States)
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We examine details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectroscopy with vacuum ultraviolet (VUV) photoionization Time-of-Flight Mass Spectrometry (TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are highlighted through findings on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with o-guaiacol as the precursor.

Research Organization:
Purdue Univ., West Lafayette, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
FG02-96ER14656
OSTI ID:
1540250
Alternate ID(s):
OSTI ID: 1468880
Journal Information:
Review of Scientific Instruments, Vol. 89, Issue 9; ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (34)

Determination of Molecular Structures from Ground State Rotational Constants journal October 1958
The photoelectron spectra and electronic structure of 2-carbonyl furans journal May 1990
Flash pyrolysis nozzle for generation of radicals in a supersonic jet expansion journal August 1992
Ultraviolet spectroscopy of fundamental lignin subunits: Guaiacol, 4-methylguaiacol, syringol, and 4-methylsyringol journal October 2013
Impact of Molecular Conformation on Barriers to Internal Methyl Rotation: The Rotational Spectrum of m -Methylbenzaldehyde journal November 2010
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry journal January 2013
Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow journal April 2015
Strong-Field Ionization of Flash Pyrolysis Reaction Products journal January 2015
Multi-resonance effects within a single chirp in broadband rotational spectroscopy: The rapid adiabatic passage regime for benzonitrile journal October 2012
Photoelectron spectroscopy of anions at 118.2nm: Observation of high electron binding energies in superhalogens MCl4− (M=Sc, Y, La) journal May 2008
Resonance-Enhanced Multiphoton Ionization and VUV-Single Photon Ionization as Soft and Selective Laser Ionization Methods for On-Line Time-of-Flight Mass Spectrometry:  Investigation of the Pyrolysis of Typical Organic Contaminants in the Steel Recycling Process journal November 2003
A chirped-pulse Fourier-transform microwave/pulsed uniform flow spectrometer. I. The low-temperature flow system journal October 2014
Microwave Spectrum, Conformational Equilibrium and Ab Initio Calculations for 2-Furanmethanol (Furfuryl Alcohol). journal January 1994
A chirped-pulse Fourier-transform microwave/pulsed uniform flow spectrometer. II. Performance and applications for reaction dynamics journal December 2014
Broadband Microwave Spectroscopy of 2-Furanyloxy Radical: Primary Pyrolysis Product of the Second-Generation Biofuel 2-Methoxyfuran journal July 2018
Microwave spectrum and structure of furfural journal November 2006
A Signature of Roaming Dynamics in the Thermal Decomposition of Ethyl Nitrite: Chirped-Pulse Rotational Spectroscopy and Kinetic Modeling journal October 2014
Perspective: The first ten years of broadband chirped pulse Fourier transform microwave spectroscopy journal May 2016
Time‐of‐Flight Mass Spectrometer with Improved Resolution journal December 1955
Determination of Molecular Structure from Microwave Spectroscopic Data journal January 1953
An overview of organic molecule soft ionization using vacuum ultraviolet laser radiation journal November 2005
Communication: A new spectroscopic window on hydroxyl radicals using UV + VUV resonant ionization journal June 2011
Identification of isomeric C5H3 and C5H5 free radicals in flame with tunable synchrotron photoionization journal June 2006
The structural and conformational properties of 2-methoxyfuran as studied by microwave spectroscopy and quantum chemical calculations journal June 2001
Structural studies of biomolecules in the gas phase by chirped-pulse Fourier transform microwave spectroscopy journal January 2011
Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy journal September 2016
The electronic states of 2-furanmethanol (furfuryl alcohol) studied by photon absorption and electron impact spectroscopies journal October 2003
Chirped-Pulse Fourier Transform Microwave Spectroscopy Coupled with a Flash Pyrolysis Microreactor: Structural Determination of the Reactive Intermediate Cyclopentadienone journal June 2014
Pyrolysis Pathways of the Furanic Ether 2-Methoxyfuran journal August 2015
Thermal Decomposition Mechanisms of the Methoxyphenols: Formation of Phenol, Cyclopentadienone, Vinylacetylene, and Acetylene journal November 2011
A broadband Fourier transform microwave spectrometer based on chirped pulse excitation journal May 2008
Measuring Picosecond Isomerization Kinetics via Broadband Microwave Spectroscopy journal May 2008
Conformer-specific microwave spectroscopy of 3-phenylpropionitrile by strong field coherence breaking journal July 2018
Chemical dynamics, molecular energetics, and kinetics at the synchrotron journal January 2010

Cited By (4)

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non‐Covalent Interactions journal July 2019
Broadband rotational spectroscopy of trans 3-pentenenitrile and 4-pentenenitrile journal January 2019
Propagating molecular rotational coherences through single-frequency pulses in the strong field regime journal August 2019
Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone journal July 2019

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