Pulsed-Field Ionization Zero-Kinetic-Energy Photoelectron Spectra of Ar2

Onuma, Takeyoshi; Yoshii, H.; Ishijima, H.; Itou, Y.; Hayaishi, T; Morioka, Y

doi:10.1006/jmsp.1999.7952

Cited by 21 publications

(14 citation statements)

References 26 publications

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“…Similar disappearance of bands in the VUV-PFI-PE spectrum has been observed for the C ( 2 Π 1/2u ) state of the Ar dimer, and it was ascribed to a short lifetime of the high-n Rydberg states with the C state as an ion core: the C state dissociates into Ar(S 0 ) + Ar + ( 2 P 1/2 ). 67 In the VUV-PFI-PE study of NO 2 , the b( 3 A 2 ) band was observed much more weakly than that observed in the He(I) UPS. 68,69 However, the present result on pyrazine is perhaps the clearest example of the significant difference between VUV-PFI-PE and UPS in observation of ionic states with short lifetimes.…”

Section: Discussionmentioning

confidence: 92%

3s Rydberg and Cationic States of Pyrazine Studied by Photoelectron Spectroscopy

et al. 2008

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We have studied 3s(n-1 and pi-1) Rydberg states and D0(n-1) and D1(pi-1) cationic states of pyrazine [1,4-diazabenzene] by picosecond (2 + 1) resonance-enhanced multiphoton ionization (REMPI), (2 + 1) REMPI photoelectron imaging, He(I) ultraviolet photoelectron spectroscopy (UPS), and vacuum ultraviolet pulsed field ionization photoelectron spectroscopy (VUV-PFI-PE). The new He(I) photoelectron spectrum of pyrazine in a supersonic jet revealed a considerably finer vibrational structure than a previous photoelectron spectrum of pyrazine vapor. We performed Franck-Condon analysis on the observed photoelectron and REMPI spectra in combination with ab initio density functional theory and molecular orbital calculations to determine the equilibrium geometries in the D0 and 3s(n-1) states. The equilibrium geometries were found to differ slightly between the D0 and 3s states, indicating the influence of a Rydberg electron on the molecular structure. The locations of the D1-D0 and 3s(pi-1)-3s(n-1) conical intersections were estimated. From the line width in the D1 <-- S0 spectrum, we estimated the lifetime of D1 to be 12 fs for pyrazine and 15 fs for fully deuterated pyrazine. A similar lifetime was estimated for the 3s(pi-1) state of pyrazine by REMPI spectroscopy. The vibrational feature of D1 observed in the VUV-PFI-PE measurement differed dramatically from that in the UPS spectrum, which suggests that the high-n Rydberg (ZEKE) states converging to the D1 vibronic state are short-lived due to electronic autoionization to the D0 continuum.

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Section: Discussionmentioning

confidence: 92%

3s Rydberg and Cationic States of Pyrazine Studied by Photoelectron Spectroscopy

et al. 2008

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“…An example, taken from the work of Onuma et al (1999), is presented in Fig. 11 and shows the photoelectron spectrum of Ar 2 in the region below the Ar 1 S 0 + Ar + 2 P 3/2 dissociation limit.…”

Section: Threshold Photoelectron Spectroscopymentioning

confidence: 99%

High‐resolution Photoelectron Spectroscopy

Merkt

Willitsch

Hollenstein

2011

Handbook of High‐resolution Spectroscopy

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The evolution of photoelectron spectroscopy of neutral molecules in the gas phase, from its first applications in the early 1960s to the present day, is reviewed with emphasis on the description of methods that have contributed to the improvement of resolution. In the early days, photoelectron spectroscopy was very successfully used to study the electronic structure of molecules. As the resolution improved, the emphasis gradually shifted to studies of the structure and dynamics of molecular cations. Current methods enable one to fully resolve the rotational structure in the photoelectron spectra of polyatomic molecules and even to measure the fine and hyperfine structures of positively charged atoms and small molecules. Several of the methods providing high resolution make use of the long lifetimes and electric‐field‐ionization properties of high Rydberg states and give access to detailed information on molecular ionization channels and molecular photoionization.

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“…The argon dimer cation is a prototypical system for these types of experiments. Its simple electronic structure and large absorption cross sections in the UV-visible region make Ar 2 + tractable by both theory and experiment [20,[25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41]. The binding energy of Ar 2 + has been the subject of numerous studies [20,29,[34][35][36][37][38][39][40] which have been summarized by Weitzel and Mӓhnert [40].…”

Section: Introductionmentioning

confidence: 99%

Velocity map ion imaging study of Ar2+ photodissociation

Maner

Mauney

Duncan

2017

Chemical Physics Letters

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The argon dimer cation is produced in a plasma generated by a laser spark in a supersonic expansion. The cold ions are mass selected and investigated by photodissociation at 355 nm, with velocity map imaging of the Ar + photofragment. Using the radius of the image, we determine the kinetic energy release and derive the ground state dissociation energy of Ar 2 + as D 0 " = 1.32 +0.03/-0.02 eV. Additionally, the angular distribution is described with β = 1.71-1.95, consistent with excitation of the parallel-type 2 Σ g + ← 2 Σ u + transition.

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Pulsed-Field Ionization Zero-Kinetic-Energy Photoelectron Spectra of Ar2

Cited by 21 publications

References 26 publications

3s Rydberg and Cationic States of Pyrazine Studied by Photoelectron Spectroscopy

3s Rydberg and Cationic States of Pyrazine Studied by Photoelectron Spectroscopy

High‐resolution Photoelectron Spectroscopy

Velocity map ion imaging study of Ar2+ photodissociation

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