High-resolution laser spectroscopy of BaOH and BaOD: Anomalous spin-orbit coupling in the (A)(2)over tilde(2)Pi state

J. D. Tandy, J. -G. Wang, P. F. Bernath

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Abstract

The (A) over bar (2)Pi(000) - (X) over bar (2)Sigma(+)(000) transition of BaOD has been rotationally analyzed using laser excitation spectroscopy. BaOD molecules were synthesized through the reaction of Ba atoms with D2O in a Broida-type oven. Rotational and fine structure parameters determined for the (A) over bar (2)Pi(000) state of BaOD yielded a spin-orbit coupling constant A significantly different from the corresponding value for BaOH (similar to 605.8 cm(-1) versus 560.1 cm(-1)). boolean AND-doubling constants for the (A) over bar (2)Pi state were observed to be in poor agreement with the predictions of the pure precession model for the interaction between the (A) over tilde (2)Pi and the (B) over tilde (2)Sigma(+) states in BaOD. Explanations for the Unusual spin-orbit splitting and apparent failure of the pure precession and unique perturber models in BaOH and BaOD are discussed. with particular reference to possible global and local perturbations arising from vibrationally excited bands of the (A) over bar'(2)Delta state. (C) 2009 Elsevier Inc, All rights reserved.

Original languageEnglish
Pages (from-to)63-67
Number of pages5
JournalJOURNAL OF MOLECULAR SPECTROSCOPY
Volume255
Issue number1
DOIs
Publication statusPublished - May 2009

Keywords

  • High-resolution
  • Laser excitation
  • BaOH
  • BaOD
  • ROTATIONAL ANALYSIS
  • DIATOMIC-MOLECULES
  • DYE-LASER
  • TRANSITION
  • SROD
  • PARAMETERS
  • MILLIMETER
  • SPECTRUM
  • CAOH

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