High-resolution laser spectroscopy of the A~(2)Pi - X~(2)Sigma(+) system of calcium hydroxyl and calcium hydroxyl-d radicals: Analysis of Renner-Teller, spin-orbit, K-type resonance and Fermi resonance interactions.
Date
1995
Authors
Li, Mingguang.
Journal Title
Journal ISSN
Volume Title
Publisher
Dalhousie University
Abstract
Description
A systematic spectroscopic investigation of the A 2pi - X˜2Sigma+ band system of CaOH and CaOD radicals has been carried out. The gas phase radicals were produced in a Broida oven. A Coherent 699-29 ring dye laser was operated in single mode. Extensive and highly precise data have been recorded using laser excitation spectroscopy and resolved fluorescence spectroscopy.
The A(000) - X˜(000) band of CaOD has been studied, yielding accurate molecular constants that are essential for further studies of excited vibrational levels. The excited vibrational levels, v1 ≤ 4 and v 2 = 2, in the X˜2Sigma + state of CaOH/CaOD have been rotationally analyzed via dispersion of the laser induced fluorescence.
High resolution analysis of the A(010) - X˜(010)/(000) and A(100)/(020) - X˜(020)/(000) bands of CaOH/CaOD has been performed. For each isotopomer, the measured line positions were fitted to a global deperturbation model that simultaneously takes account of the Renner-Teller, spin-orbit and K-type resonance or Fermi resonance interactions occurring in the A2pi state. The present work has obtained the largest data base with high precision for a linear molecule exhibiting these interactions, and has accomplished the most comprehensive and rigorous matrix deperturbations.
Employing the equilibrium rotational constants determined for the two isotopic molecules, the molecular equilibrium bond lengths in both the A and X˜ states have been calculated.
In the present work, the Renner-Teller parameters, Fermi resonance parameters, Coriolis coupling constants and the molecular force field have been determined, for the first time, for an alkaline earth monohydroxide molecule.
Thesis (Ph.D.)--Dalhousie University (Canada), 1995.
The A(000) - X˜(000) band of CaOD has been studied, yielding accurate molecular constants that are essential for further studies of excited vibrational levels. The excited vibrational levels, v1 ≤ 4 and v 2 = 2, in the X˜2Sigma + state of CaOH/CaOD have been rotationally analyzed via dispersion of the laser induced fluorescence.
High resolution analysis of the A(010) - X˜(010)/(000) and A(100)/(020) - X˜(020)/(000) bands of CaOH/CaOD has been performed. For each isotopomer, the measured line positions were fitted to a global deperturbation model that simultaneously takes account of the Renner-Teller, spin-orbit and K-type resonance or Fermi resonance interactions occurring in the A2pi state. The present work has obtained the largest data base with high precision for a linear molecule exhibiting these interactions, and has accomplished the most comprehensive and rigorous matrix deperturbations.
Employing the equilibrium rotational constants determined for the two isotopic molecules, the molecular equilibrium bond lengths in both the A and X˜ states have been calculated.
In the present work, the Renner-Teller parameters, Fermi resonance parameters, Coriolis coupling constants and the molecular force field have been determined, for the first time, for an alkaline earth monohydroxide molecule.
Thesis (Ph.D.)--Dalhousie University (Canada), 1995.
Keywords
Chemistry, Physical.