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Title: Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling

Abstract

A cryogenic octopole accumulation trap (COAT) has been coupled to a photoelectron-photofragment coincidence (PPC) spectrometer allowing for improved control over anion vibrational excitation. The anions are heated and cooled via collisions with buffer gas <17 K. Shorter trapping times (500 μs) prevent thermalization and result in anions with high internal excitation while longer trapping times (80 ms) at cryogenic temperatures thermalize the ions to the temperature of the buffer gas. The capabilities of the COAT are demonstrated using PPC spectroscopy of O-3 at 388 nm (Ehν = 3.20 eV). Cooling the precursor anions with COAT resulted in the elimination of the autodetachment of vibrationally excited O-2 produced by the photodissociation O-3 + hν → O + O-2(v ≥ 4). Under heating conditions, a lower limit temperature for the anions was determined to be 1,500 K through Franck-Condon simulations of the photo-detachment spectrum of O-3, considering a significant fraction of the ions undergo photodissociation in competition with photo-detachment. The ability to cool or heat ions by varying ion injection and trapping duration in COAT provides a new flexibility for studying the spectroscopy of cold ions as well as thermally activated processes.

Authors:
; ; ;
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1509921
Alternate Identifier(s):
OSTI ID: 1614602; OSTI ID: 1755314
Grant/Contract Number:  
FG03-98ER14879
Resource Type:
Published Article
Journal Name:
Frontiers in Chemistry
Additional Journal Information:
Journal Name: Frontiers in Chemistry Journal Volume: 7; Journal ID: ISSN 2296-2646
Publisher:
Frontiers Research Foundation
Country of Publication:
Switzerland
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; Chemistry; ion trap; ozonide; photoelectron; photofragment; coincidence spectroscopy; collisional excitation; buffer gas cooling; ozone; photodetachment; radiofrequency octopole ion trap; radiofrequency octopole ion trap, buffer gas cooling, ozonide, photodetachment

Citation Formats

Shen, Ben B., Lunny, Katharine G., Benitez, Yanice, and Continetti, Robert E. Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling. Switzerland: N. p., 2019. Web. doi:10.3389/fchem.2019.00295.
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Shen, Ben B., Lunny, Katharine G., Benitez, Yanice, & Continetti, Robert E. Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling. Switzerland. https://doi.org/10.3389/fchem.2019.00295
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Shen, Ben B., Lunny, Katharine G., Benitez, Yanice, and Continetti, Robert E. Tue . "Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling". Switzerland. https://doi.org/10.3389/fchem.2019.00295.
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@article{osti_1509921,
title = {Photoelectron-Photofragment Coincidence Spectroscopy With Ions Prepared in a Cryogenic Octopole Accumulation Trap: Collisional Excitation and Buffer Gas Cooling},
author = {Shen, Ben B. and Lunny, Katharine G. and Benitez, Yanice and Continetti, Robert E.},
abstractNote = {A cryogenic octopole accumulation trap (COAT) has been coupled to a photoelectron-photofragment coincidence (PPC) spectrometer allowing for improved control over anion vibrational excitation. The anions are heated and cooled via collisions with buffer gas <17 K. Shorter trapping times (500 μs) prevent thermalization and result in anions with high internal excitation while longer trapping times (80 ms) at cryogenic temperatures thermalize the ions to the temperature of the buffer gas. The capabilities of the COAT are demonstrated using PPC spectroscopy of O-3 at 388 nm (Ehν = 3.20 eV). Cooling the precursor anions with COAT resulted in the elimination of the autodetachment of vibrationally excited O-2 produced by the photodissociation O-3 + hν → O + O-2(v ≥ 4). Under heating conditions, a lower limit temperature for the anions was determined to be 1,500 K through Franck-Condon simulations of the photo-detachment spectrum of O-3, considering a significant fraction of the ions undergo photodissociation in competition with photo-detachment. The ability to cool or heat ions by varying ion injection and trapping duration in COAT provides a new flexibility for studying the spectroscopy of cold ions as well as thermally activated processes.},
doi = {10.3389/fchem.2019.00295},
journal = {Frontiers in Chemistry},
number = ,
volume = 7,
place = {Switzerland},
year = {Tue Apr 30 00:00:00 EDT 2019},
month = {Tue Apr 30 00:00:00 EDT 2019}
}
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https://doi.org/10.3389/fchem.2019.00295
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