Rotationally resolved threshold photoelectron spectroscopy of O2 using coherent XUV: formation of vibrationally excited ions in the Franck–Condon gap

1994 ◽  
Vol 72 (11-12) ◽  
pp. 1284-1293 ◽  
Author(s):  
W. Kong ◽  
J. W. Hepburn
Keyword(s):  
Light Source ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectrum ◽  
Extreme Ultraviolet ◽  
Photoelectron Spectra ◽  
Vibrationally Excited ◽  
Wide Range ◽  
Vibrational Levels ◽  
Franck Condon ◽  
Dissociative State

The rotationally resolved photoelectron spectrum of high vibrational levels of O2+ in the Franck–Condon gap was investigated using pulsed field ionization, zero kinetic energy photoelectron spectroscopy. By using a coherent extreme ultraviolet light source for single-photon excitation, the ν+ = 6–24 vibrational levels of O2+X2Πg were studied. This is the first time levels higher than ν+ = 14 have been observed with rotational resolution. The highest level studied in the present work had a vibrational energy corresponding to 70% of the well depth. Along with the novelty of the spectroscopic technique, the present results reveal interesting and new ionization dynamics. All levels observed are Franck–Condon forbidden, and are not observed in a conventional photoelectron spectrum. There was no direct relation between the vibrational bands and the autoionizing states observed in the photoionization efficiency spectrum in the same energy region, and the rotational line intensities observed in the various bands in the current threshold photoelectron spectra were all similar. The mechanism of this process was different from the "resonant autoionization" model, which involves coupling between a Rydberg state with a low principal quantum number, a dissociative state, arid the Rydberg series converging to the vibrationally excited ion states. Instead, the excitation process was believed to be more direct, involving mainly a dissociative state (or states) and the Rydberg states with a vibrationally excited ion core. Further investigation of this mechanism is still necessary, but the formation of these highly vibrationally excited ions opens a new horizon in state-selective reaction dynamics. With the coherent XUV light source and the PFI-ZEKE technique, a wide range of vibrational energies (up to 4 eV) can be deposited into the O2+ reactant with rovibrational selectivity.

A Discussion on photoelectron spectroscopy - Franck-Condon factors and autoionization in the photoelectron spectra of diatomic molecules

1970 ◽  
Vol 268 (1184) ◽  
pp. 159-162 ◽  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Photoionization Cross Section ◽  
Resonance Wavelength ◽  
Exciting Radiation ◽  
Vibrational Structure ◽  
Photoelectron Spectra ◽  
Condon Factors ◽  
Franck Condon ◽  
Characteristic Manner ◽  
Good Agreement

Distributions of calculated Franck-Condon factors for autoionizing transitions are used to illustrate the way in which the vibrational structure of the photoelectron spectrum may be extended in a characteristic manner when the wavelength of the exciting radiation coincides with a resonance in the photoionization cross section of a diatomic gas. The calculations are found to be in good agreement with resonance wavelength photoelectron spectra from O2.

scholarly journals Photoelectron spectroscopy of reactive intermediates

1988 ◽  
Vol 324 (1578) ◽  
pp. 197-207 ◽  
Keyword(s):  
Transition Metal ◽  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectrum ◽  
Reactive Intermediates ◽  
Vapour Phase ◽  
Photoelectron Spectra ◽  
Triatomic Molecule ◽  
Recent Developments ◽  
Vanadium Monoxide

Recent developments in the use of photoelectron spectroscopy to study reactive intermediates in the gas phase are reviewed. The information to be derived on low-lying cationic states from such studies is illustrated by considering two diatomic molecules, NCI and PF, and one triatomic molecule, HNO. Also, the use of a transition-metal photoelectron spectrum to interpret the photoelectron spectrum of the corresponding transition-metal oxide is discussed by using the spectra of vanadium and vanadium monoxide as examples. The value of super-heating in high-temperature photoelectron spectroscopy is demonstrated by considering the vapour-phase photoelectron spectra of the monomers and dimers of sodium hydroxide.

scholarly journals An experimental and computational study of the effect of aqueous solution on the multiphoton ionisation photoelectron spectrum of phenol

2020 ◽  
Vol 221 ◽  
pp. 202-218 ◽  
Author(s):  
Alice Henley ◽  
Jamie W. Riley ◽  
Bingxing Wang ◽  
Helen H. Fielding
Keyword(s):  
Aqueous Solution ◽  
Inelastic Scattering ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectrum ◽  
Computational Study ◽  
Inhomogeneous Broadening ◽  
Solution Phase ◽  
Photoelectron Spectra ◽  
The Impact

We revisit the photoelectron spectroscopy of aqueous phenol in an effort to improve our understanding of the impact of inhomogeneous broadening and inelastic scattering on solution-phase photoelectron spectra.

TRANSFORMATION OF THE ELECTRONIC STRUCTURE OF Cu INTO Cu2O IN THE ADSORPTION OF OXYGEN

1999 ◽  
Vol 06 (03n04) ◽  
pp. 383-388 ◽  
Author(s):  
V. P. BELASH ◽  
I. N. KLIMOVA ◽  
V. I. KORMILETS ◽  
V. YU. TRUBITSIN ◽  
L. D. FINKELSTEIN
Keyword(s):  
Electronic Structure ◽  
Photoelectron Spectroscopy ◽  
Surface Oxidation ◽  
Oxygen Adsorption ◽  
Copper Surface ◽  
Photoelectron Spectra ◽  
Orbital Method ◽  
Full Potential ◽  
Wide Range ◽  
Pure Cu

Systematic photoelectron-spectroscopy studies of the oxygen adsorption on a polycrystalline copper in a wide range of oxygen exposures allowed us to trace the step-by-step transformation of the electronic structure of pure Cu into the electronic structure of Cu 2 O . With the use of the density-of-states calculations implemented by the full-potential linear muffin-tin-orbital method, the interpretation of a number of features in the photoelectron spectra and their behavior with the increase of oxygen exposure was carried out. It was also shown that copper-surface oxidation proceeds in three main steps.

scholarly journals Binding energy of solvated electrons and retrieval of true UV photoelectron spectra of liquids

2019 ◽  
Vol 5 (8) ◽  
pp. eaaw6896 ◽  
Author(s):  
Junichi Nishitani ◽  
Yo-ichi Yamamoto ◽  
Christopher W. West ◽  
Shutaro Karashima ◽  
Toshinori Suzuki
Keyword(s):  
Binding Energy ◽  
Photoelectron Spectroscopy ◽  
Extreme Ultraviolet ◽  
High Harmonic ◽  
Chemical Species ◽  
Electronic Energy ◽  
Photoelectron Spectra ◽  
Solvated Electrons ◽  
Energy Distributions ◽  
Uv Photoelectron Spectroscopy

The electronic energy and dynamics of solvated electrons, the simplest yet elusive chemical species, is of interest in chemistry, physics, and biology. Here, we present the electron binding energy distributions of solvated electrons in liquid water, methanol, and ethanol accurately measured using extreme ultraviolet (EUV) photoelectron spectroscopy of liquids with a single-order high harmonic. The distributions are Gaussian in all cases. Using the EUV and UV photoelectron spectra of solvated electrons, we succeeded in retrieving sharp electron kinetic energy distributions from the spectra broadened and energy shifted by inelastic scattering in liquids, overcoming an obstacle in ultrafast UV photoelectron spectroscopy of liquids. The method is demonstrated for the benchmark systems of charge transfer to solvent reaction and ultrafast internal conversion of hydrated electron from the first excited state.

High Resolution Photoelectron Spectroscopy of Cryogenically-Cooled NO3ˉ

2019 ◽  
Author(s):  
Mark Babin ◽  
Jessalyn DeVine ◽  
John F. Stanton ◽  
Daniel Neumark ◽  
Martin DeWitt
Keyword(s):  
High Resolution ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectra ◽  
Velocity Map Imaging ◽  
Vibrational Assignment ◽  
Neutral Radical ◽  
Resolution Measurement ◽  
Energy Dependent ◽  
Franck Condon ◽  
Insight Into

<p></p><p>High-resolution anion photoelectron spectra of cryogenically cooled NO<sub>3</sub>ˉ anions obtained using slow photoelectron velocity-map imaging are presented and provide new insight into the vibronic structure of the corresponding neutral radical. A combination of improved spectral resolution, measurement of energy-dependent intensity effects, temperature control, and comparison to theory allows for full assignment of the vibronic features observed in this spectrum. We obtain a refined electron affinity of 3.9289(14) eV for NO<sub>3</sub>. Further, the appearance of Franck-Condon forbidden transitions from vibrationally cold anions to neutral states with excitation along the NO<sub>3</sub> <i>v</i><sub>4</sub> mode confirms that these features arise from vibronic coupling with the excited state of NO<sub>3</sub> and are not hot bands as has been suggested. Together, the suite of experimental and simulated results provides clear evidence that the <i>v</i><sub>3</sub> fundamental of NO<sub>3</sub> resides near 1050 cm<sup>−1</sup>, addressing a long-standing controversy surrounding this vibrational assignment.</p> <p> </p><br><p></p>

High Resolution Photoelectron Spectroscopy of Cryogenically-Cooled NO3ˉ

2019 ◽  
Author(s):  
Mark Babin ◽  
Jessalyn DeVine ◽  
John F. Stanton ◽  
Daniel Neumark ◽  
Martin DeWitt
Keyword(s):  
High Resolution ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectra ◽  
Velocity Map Imaging ◽  
Vibrational Assignment ◽  
Neutral Radical ◽  
Resolution Measurement ◽  
Energy Dependent ◽  
Franck Condon ◽  
Insight Into

<p></p><p>High-resolution anion photoelectron spectra of cryogenically cooled NO<sub>3</sub>ˉ anions obtained using slow photoelectron velocity-map imaging are presented and provide new insight into the vibronic structure of the corresponding neutral radical. A combination of improved spectral resolution, measurement of energy-dependent intensity effects, temperature control, and comparison to theory allows for full assignment of the vibronic features observed in this spectrum. We obtain a refined electron affinity of 3.9289(14) eV for NO<sub>3</sub>. Further, the appearance of Franck-Condon forbidden transitions from vibrationally cold anions to neutral states with excitation along the NO<sub>3</sub> <i>v</i><sub>4</sub> mode confirms that these features arise from vibronic coupling with the excited state of NO<sub>3</sub> and are not hot bands as has been suggested. Together, the suite of experimental and simulated results provides clear evidence that the <i>v</i><sub>3</sub> fundamental of NO<sub>3</sub> resides near 1050 cm<sup>−1</sup>, addressing a long-standing controversy surrounding this vibrational assignment.</p> <p> </p><br><p></p>

scholarly journals Ultrafast extreme ultraviolet photoemission without space charge

2019 ◽  
Vol 205 ◽  
pp. 02014
Author(s):  
Peng Zhao ◽  
Christopher Corder ◽  
Jin Bakalis ◽  
Xinlong Li ◽  
Matthew D. Kershis ◽  
...  
Keyword(s):  
Space Charge ◽  
Photoelectron Spectroscopy ◽  
Extreme Ultraviolet ◽  
High Harmonic ◽  
Photoelectron Spectra ◽  
Time Resolved ◽  
Record Time ◽  
Free Sample ◽  
Harmonic Source

We present photoelectron spectroscopy experiments using an 88 MHz cavityenhanced high-harmonic source operating from 8 to 40 eV. Nanoampere space-charge free sample photo currents enable us to record time-resolved photoelectron spectra from weakly excited samples.

A Discussion on photoelectron spectroscopy - The role of autoionization in molecular photoelectron spectra

1970 ◽  
Vol 268 (1184) ◽  
pp. 169-175 ◽  
Keyword(s):  
Excitation Energy ◽  
Relative Intensity ◽  
Intensity Distribution ◽  
Configuration Interaction ◽  
Photoelectron Spectroscopy ◽  
Photoelectron Spectra ◽  
Final States ◽  
Condon Factors ◽  
Franck Condon

The Fano-Mies theory of configuration interaction is applied to the photoionization of diatomic molecules, yielding an expression which gives the relative intensity of vibrational peaks in photoelectron spectra when one or more autoionizing states are in the vicinity of the excitation energy. In some cases the vibrational intensity distribution depends only on Franck-Condon factors connecting autoionizing and final states. Illustrative calculations for O2 show the transition from this limit to the limit of direct photoionization as the line profile index decreases.

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