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Infrared Spectroscopy of H3O+: The ν1 Fundamental Band

✍ Scribed by Jian Tang; Takeshi Oka

Publisher
Elsevier Science
Year
1999
Tongue
English
Weight
275 KB
Volume
196
Category
Article
ISSN
0022-2852

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✦ Synopsis

The infrared spectrum of H 3 O ϩ in positive column discharges of H 2 /O 2 gas mixtures has been studied by a difference frequency laser spectrometer. The 1 fundamental band of H 3 O ϩ was identified in the region of the strong 3 Ϯ 4 0 Ϯ bands. Molecular constants were obtained by the least-squares fitting of the observed frequencies, and band origins of the 1 ϩ 4 0 Ϫ and 1 Ϫ 4 0 ϩ subbands were determined to be 3389.656(2) and 3491.170(2) cm Ϫ1 , respectively. During this study, assignment of the 3 fundamental band was extended to higher J, K transitions, which do not fit to the calculated pattern well, but have definitely been assigned by using the ground state combination differences and relative intensities. Vibration-rotation interactions between the 1 and 3 states have been considered, which explained some large discrepancies between observed and calculated frequencies and led to the identification of forbidden transitions. Energy differences in the ground state between the ⌬K ϭ 3 rotational levels were obtained from the combination differences of the forbidden and allowed transitions, which led to an accurate determination of C and D K . Equilibrium structure of H 3 O ϩ has been derived to be r e ϭ 0.974(1) Å and ␣ e ϭ 113.6(1)°.

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