Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions

Marissa L. Weichman, Daniel M. Neumark

Research output: Contribution to journalArticlepeer-review

62 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)101-124
Number of pages24
JournalAnnual Review of Physical Chemistry
StatePublished - Apr 20 2018
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Medicine


  • Anion photoelectron spectroscopy
  • Cryogenic cooling
  • High-resolution photoelectron imaging
  • Transition state spectroscopy
  • Velocity-map imaging
  • Vibronic structure


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