The permanent electric dipole moment of CaOH

Charles W. Bauschlicher, Stephen R. Langhoff, Timothy Steimle, Jeffrey E. Shirley

Research output: Contribution to journalArticlepeer-review

44 Scopus citations

Abstract

Theoretical calculations yield electric dipole moments (μ) of 0.98, 0.49, and 0.11 Debye at the computed equilibrium geometries of the X 2Σ+, A 2Π, and B 2Σ + states of CaOH. Thus the pure rotational spectra in these electronic states are expected to be weaker than the corresponding alkaline monohalides. This is consistent with our failure to observe the pure rotational spectrum of the X 2Σ+ state by microwave-optical double resonance spectroscopy, and is in agreement with our experimental determination of μ<1 D for the A 2II3/2 state. However, the vibrational-rotational spectrum is quite strong, since dμ/dr is quite large in these ionic molecules. Using the free-ion polarizabilities, the modified Rittner model predicts aμ value of about -8 D for the X 2Σ+ state, which is in error by about 9 D. The theoretical values for total dipole moment, as well as contributions from Ca+ and OH-, can be reproduced using effective polarizabilities. However, this analysis shows that the effective polarizability of OH- is a much smaller fraction of the free-ion value than for Ca+, because Pauli repulsion restricts the OH- polarization toward the Ca+. Some account of this effect seems to be a prerequisite for the successful application of either Rittner or ligand field models to ionic systems.

Original languageEnglish (US)
Pages (from-to)4179-4186
Number of pages8
JournalThe Journal of chemical physics
Volume93
Issue number6
DOIs
StatePublished - Jan 1 1990

ASJC Scopus subject areas

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

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