Far-wing excitation study of the reactions in the Hg-H 2 collisional quasimolecules. I. Transit-state selectivity in HgH formation and three-body dissociation

K. Ohmori, T. Takahashi, H. Chiba, K. Saito, T. Nakamura, Misaki Okunishi, Kiyoshi Ueda, Y. Sato

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6 Citations (Scopus)

Abstract

Laser-pump/probe and double-beam absorption/dispersion approaches have been applied to the far wings of the Hg 3 P 1 - 1 S 0 resonance line broadened by collisions with H 2 . Absolute reduced absorption coefficients of the Hg-H 2 quasimolecules have been determined as a function of the wave-number shift A from the resonance-line center both in the red and blue wings. Decay probabilities of the excited Hg*( 3 P 1 )-H 2 quasimolecule into the reactive channel (HgH formation) or into the elastic channel (Hg*( 3 P 1 ) formation) have been determined as a function of A both for the red-wing excited à and blue-wing excited B̃ states. The rest of these decay probabilities have been attributed to three-body dissociation Hg( 1 S 0 )+H+H. These results indicate that (a) the Ã-state surface serves more effectively in HgH formation than the B̃-state surface by a factor of about 2.3; but (b) three-body dissociation, in turn, proceeds far more efficiently on the B̃-state surface than on the Ã-state surface. Discussions about the. energy barriers and the orbital correlations for HgH formation are presented, based on the Δ dependence of these decaying probabilities.

Original languageEnglish
Pages (from-to)7464-7473
Number of pages10
JournalJournal of Chemical Physics
Volume105
Issue number17
DOIs
Publication statusPublished - 1996 Jan 1

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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