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Title: Vacuum Ultraviolet Photoionization of Complex Chemical Systems

Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems in this paper. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion–molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. Finally, new directions in coupling VUV radiation to interrogate complex chemical systems are discussed.
Authors:
 [1] ;  [1] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Annual Review of Physical Chemistry
Additional Journal Information:
Journal Volume: 67; Journal Issue: 1; Journal ID: ISSN 0066-426X
Publisher:
Annual Reviews
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 43 PARTICLE ACCELERATORS; mass spectrometry; synchrotron; hydrogen bonds; combustion; proton transfer; laser ablation; thermochemistry; electronic structure
OSTI Identifier:
1456939

Kostko, Oleg, Bandyopadhyay, Biswajit, and Ahmed, Musahid. Vacuum Ultraviolet Photoionization of Complex Chemical Systems. United States: N. p., Web. doi:10.1146/annurev-physchem-040215-112553.
Kostko, Oleg, Bandyopadhyay, Biswajit, & Ahmed, Musahid. Vacuum Ultraviolet Photoionization of Complex Chemical Systems. United States. doi:10.1146/annurev-physchem-040215-112553.
Kostko, Oleg, Bandyopadhyay, Biswajit, and Ahmed, Musahid. 2016. "Vacuum Ultraviolet Photoionization of Complex Chemical Systems". United States. doi:10.1146/annurev-physchem-040215-112553. https://www.osti.gov/servlets/purl/1456939.
@article{osti_1456939,
title = {Vacuum Ultraviolet Photoionization of Complex Chemical Systems},
author = {Kostko, Oleg and Bandyopadhyay, Biswajit and Ahmed, Musahid},
abstractNote = {Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems in this paper. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion–molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. Finally, new directions in coupling VUV radiation to interrogate complex chemical systems are discussed.},
doi = {10.1146/annurev-physchem-040215-112553},
journal = {Annual Review of Physical Chemistry},
number = 1,
volume = 67,
place = {United States},
year = {2016},
month = {2}
}