TY - JOUR
T1 - Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions
AU - Weichman, Marissa L.
AU - Neumark, Daniel M.
N1 - Funding Information:
The authors acknowledge support from the Air Force Office of Scientific Research under grant FA9550-16-1-0097 and from the Director, Office of Basic Energy Sciences, Chemical Sciences Division of the US Department of Energy under contract DE-AC02-05CH11231. M.L.W. thanks the National Science Foundation for a graduate research fellowship.
Publisher Copyright:
© 2018 by Annual Reviews. All rights reserved.
PY - 2018/4/20
Y1 - 2018/4/20
N2 - Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1-2 cm-1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.
AB - Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1-2 cm-1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.
KW - Anion photoelectron spectroscopy
KW - Cryogenic cooling
KW - High-resolution photoelectron imaging
KW - Transition state spectroscopy
KW - Velocity-map imaging
KW - Vibronic structure
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U2 - 10.1146/annurev-physchem-050317-020808
DO - 10.1146/annurev-physchem-050317-020808
M3 - Article
C2 - 29401036
AN - SCOPUS:85045958891
SN - 0066-426X
VL - 69
SP - 101
EP - 124
JO - Annual Review of Physical Chemistry
JF - Annual Review of Physical Chemistry
ER -