Superexcitation and subsequent decay of triatomic molecules studied by two-dimensional photoelectron spectroscopy

Koichiro Mitsuke, Hideo Hattori, Yasumasa Hikosaka

研究成果: ジャーナルへの寄稿学術論文査読

4 被引用数 (Scopus)

抄録

Photoionization and photodissociation processes of SO2 and CS2 in vacuum UV are studied by using two-dimensional photoelectron spectroscopy with a monochromatized synchrotron radiation source. The principal focus is on the mechanisms of autoionization and neutral dissociation of superexcited states. Photoelectron spectra of SO2 exhibit characteristic peaks at the electron kinetic energy below 1.8 eV which are assigned as resulting from autoionizing transitions of excited atomic sulfur, S*, into the ground S+(4S°) state. These S* atoms are in the singlet Rydberg states converging to S+(2D°). The precursor molecular states, SO*2, are considered to be multiple-electron excited Rydberg states lying at the photon energy above approximately 22 eV. The onset of the photoelectron yield due to the atomic autoionization accords with that expected from the thermochemical threshold for the formation of S* through three-body dissociation SO*2→S*+O+O. The two-dimensional photoelectron spectrum of CS2 provides tangible evidence for the formation of a dipole-forbidden Rydberg state (6σg)-1(3dσg)11Σg+ at the photon energy of 14.88 eV which autoionizes into the v3 = 1 vibrational state of the antisymmetric stretch v3 mode of CS2+ (X2Πg,Ω, Ω = 1/2 and 3/2). This Rydberg state is expected to borrow substantial oscillator strength from the (6σg)-1(5pσu)11Σu+ state through vibronic coupling involving the v3 vibration.

本文言語英語
ページ(範囲)137-150
ページ数14
ジャーナルJournal of Electron Spectroscopy and Related Phenomena
112
1-3
DOI
出版ステータス出版済み - 2000/11

ASJC Scopus 主題領域

  • 電子材料、光学材料、および磁性材料
  • 放射線
  • 原子分子物理学および光学
  • 凝縮系物理学
  • 分光学
  • 物理化学および理論化学

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