Photodetachment Imaging Study of the Vinoxide Anion

Bowen, M. Shane; Continetti, Robert E.

doi:10.1021/jp040083w

Cited by 34 publications

(51 citation statements)

References 34 publications

(58 reference statements)

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“…Photoelectron spectra of the vinoxide anion have been reported by Ellison et al 13 and Continetti and co-workers. 14,15 The spectrum of Ellison et al yielded a value of 1.817Ϯ 0.023 eV for the EA of C 2 H 3 O, in agreement with the value obtained by Zimmerman et al 35 via measurement of the photodetachment cross section, and showed a partially resolved vibrational progression with a 500 cm −1 peak spacing that was attributed to the CCO bending mode of the radical X state. The more recent photoelectron spectrum by Alconcel et al 14 at higher photon energy ͑3.55 eV͒ and better resolution exhibited transitions to the radical X and Ã states, yielding an EA of 1.795Ϯ 0.015 eV and a term energy T 0 = 1.015Ϯ 0.015 eV for the Ã state.…”

Section: Introductionsupporting

confidence: 76%

“…We obtain improved values for the electron affinity ͑EA͒ and first excited state term energy of the vinoxy radical. The SEVI spectra show considerably more vibrational structure than previous anion photoelectron spectra, [13][14][15] leading to new assignments of vibrational modes in the anion and neutral.…”

Section: Introductionmentioning

confidence: 76%

“…3, consistent with earlier results. 15 Though only a few traces are shown for clarity, several scans were taken at progressively lower photon energies in order to achieve high resolution for all peaks. Peak positions are taken from the highest resolution scan taken for that peak.…”

Section: Resultsmentioning

confidence: 99%

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Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Yacovitch

Garand

Neumark

2009

The Journal of Chemical Physics

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High resolution photoelectron spectra of the vinoxide anion are obtained by slow electron velocity-map imaging. Transitions between the anion X (1)A(') ground electronic state and the radical X (2)A(") and A (2)A(') states are observed. This experiment yields a precise value of 1.8250+/-0.0012 eV for the adiabatic electron affinity and 0.996+/-0.003 eV for the A-X term energy of the vinoxy radical. Franck-Condon simulations of the X (2)A(") <-- X (1)A(') transition are performed at varying levels of approximation. Full treatment with Duschinsky rotation is necessary to reproduce experimental results. Comparison of the experimental and simulated spectra leads to the assignment of previously unresolved transitions, notably between levels of a(") symmetry.

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Section: Introductionsupporting

confidence: 76%

Section: Introductionmentioning

confidence: 76%

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Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Yacovitch

Garand

Neumark

2009

The Journal of Chemical Physics

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“…In theX 2 A 00 portion of the spectrum, the β value for the VO system is -0.7 ( 0.1, 99 which well matches that for the 1-MVO system, -0.75 ( 0.05. On the other hand, the positive β value, þ0.6 ( 0.1, forÃ 2 A 0 VO radical 99 is in stark contrast to the negative one, -0.60 ( 0.05, for A 2 A 0 1-MVO radical. Figure S1 in the Supporting Information shows that the π MO of the 1-MVO ion has only a minor contribution from the methyl group, and it does not much differ from that of the VO ion.…”

Section: Vibronic Structure Of the 1-methylvinoxy Radicalsupporting

confidence: 57%

Photoelectron Spectroscopic Study of the Oxyallyl Diradical

et al. 2011

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ABSTRACT:The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O •-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states ( 3 B 2 and 3 B 1 ) of OXA and the ground doublet state ( 2 A 2 ) of the radical anion using density functional theory (DFT). Spectral simulations have been carried out for the triplet states based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the 3 B 2 state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the 3 B 2 feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the 3 B 2 state. Complete active space selfconsistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ( 1 A 1 ) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the 1 A 1 state and its vibrational progression of the CO stretching mode. The 1 A 1 state is the lowest electronic state of OXA, and the electron affinity (EA) of OXA is 1.940 ( 0.010 eV. The 3 B 2 state is the first excited state with an electronic term energy of 55 ( 2 meV. The widths of the vibronic peaks of theX 1 A 1 state are much broader than those of theã 3 B 2 state, implying that the 1 A 1 state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the 1 A 1 state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cyclopropanone. The simulation ofb 3 B 1 OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the 3 B 1 state is 0.883 ( 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O •-reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to theX 3 A 00 state of AC. The ground ( 2 A 00 ) and first excited ( 2 A 0 ) states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

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“…This "high-throughput photoelectron spectroscopy" mode has led, for example, to the extraction of NO − (CD 4 ) and NO − (H 2 O) spectra 39 from an experiment performed on the DOCO − anion. An example of this extraction is outlined in Figure 12, with photoelectron images and spectra extracted from peaks in the fragment TOF spectrum corresponding to the vinoxide (C 2 H 3 O − ) anion 40 and NO 2 − , both of which are trapped simultaneously. No detectable crosstalk between the spectra of the two species is seen, allowing photoelectron spectra of multiple species to be collected in a survey experiment.…”

Section: E Multimass Experimentsmentioning

confidence: 99%

Photoelectron-photofragment coincidence spectroscopy in a cryogenically cooled linear electrostatic ion beam trap

Johnson

Shen

Poad

et al. 2011

Review of Scientific Instruments

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A cryogenically cooled linear electrostatic ion beam trap for use in photoelectron-photofragment coincidence (PPC) spectroscopy is described. Using this instrument, anions created in cold, low-duty-cycle sources can be stored for many seconds in a ~20 K environment to cool radiatively, removing energetic uncertainties due to vibrationally excited precursor anions. This apparatus maintains a well-collimated beam necessary for high-resolution fragment imaging and the high experimental duty cycle needed for coincidence experiments. Ion oscillation is bunched and phase-locked to a modelocked laser, ensuring temporal overlap between ion bunches and laser pulses and that ions are intersected by the laser only when travelling in one direction. An electron detector is housed in the field-free center of the trap, allowing PPC experiments to be carried out on ions while they are stored and permitting efficient detection of 3-dimensional electron and neutral recoil trajectories. The effects of trapping parameters on the center-of-mass trajectories in the laser-ion interaction region are explored to optimize neutral particle resolution, and the impact of bunching on ion oscillation is established. Finally, an initial demonstration of radiative cooling is presented.

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Photodetachment Imaging Study of the Vinoxide Anion

Cited by 34 publications

References 34 publications

Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Photoelectron Spectroscopic Study of the Oxyallyl Diradical

Photoelectron-photofragment coincidence spectroscopy in a cryogenically cooled linear electrostatic ion beam trap

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