Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 125, Issue 33, Pages 7260-7265Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.1c05514
Keywords
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Funding
- Air Force Office of Scientific Research [FA9550-19-1-0051]
- AFOSR's Defense University Research Instrumentation Program [FA9550-19-1-0139]
- Army Research Office
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This study investigates the effect of vibrational pre-excitation of anions on their photoelectron spectra using a new method called IR cryo-SEVI, which combines cryogenic cooling of anions with slow photoelectron velocity-map imaging and tunable IR radiation. The results on OH- demonstrate that vibrational excitation leads to different photodetachment signals and transitions, highlighting the importance of vibrational dynamics in anion photoelectron spectroscopy.
The effect of vibrational pre-excitation of anions on their photoelectron spectra is explored, combining slow photoelectron velocity-map imaging of cryogenically cooled anions (cryo-SEVI) with tunable IR radiation to pre-excite the anions. This new IR cryo-SEVI method is applied to OH- as a test system, where the R(0) transition of the hydroxyl anion (3591.53 cm(-1)) is pumped. Vibrational excitation induces a 30% depletion in photodetachment signal from the v = 0, J = 0 ground state of the anion and the appearance of all five allowed, rotationally resolved photodetachment transitions from the OH- (v = 1, J = 1) level, each with peak widths between 1 and 2 cm(-1). By scanning the IR laser, IR cryo-SEVI can also serve as a novel action technique to obtain the vibrational spectrum of OH-, giving an experimental value for the R(0) transition of 3591(1.2) cm(-1).
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