A combined experimental/theoretical investigation of the He + ICl interactions: Determination of the binding energies of the T-shaped and linear He⋯I35Cl(X,ν″ = 0) conformers

David S. Boucher, Joshua P. Darr, Matthew D. Bradke, Richard A. Loomis, Anne B. McCoy

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Abstract

A simple model based on the assumption of a thermodynamic equilibrium between the populations of the T-shaped and linear He⋯I 35Cl(X,ν″ = 0) complexes stabilized in a supersonic expansion is utilized to estimate the relative binding energies of the ground state conformers. In this model, the relative intensities of the laser-induced fluorescence features, attributed to transitions of each conformer, are used to track changes in the populations along the expansion. The relative intensities of the features and the I35Cl(X,ν″ = 0) rotational temperatures measured at each distance are fit to ratios of the quantum mechanical partition functions for the T-shaped and linear complexes. These are used to determine the difference between the binding energies of the two conformers. The linear He⋯I35Cl(X,ν″ = 0) complex is estimated to be 2.5(6) cm-1 more strongly bound than the T-shaped conformer. The validity of this model was in part confirmed by performing the analysis on calculated ro-vibronic spectra of He⋯I35Cl, where the J″ = 0 binding energies of the ground state conformers are known. The results from high-resolution action and two-color pump-probe spectroscopy experiments reveal that the binding energy of the linear He⋯I 35Cl(X,ν″ = 0) conformer is precisely 22.0(2) cm -1. The binding energy of the T-shaped He⋯I 35Cl(X,ν″ = 0) conformer is then 19.5(6) cm-1.

Original languageEnglish (US)
Pages (from-to)5275-5282
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume6
Issue number23
DOIs
StatePublished - Dec 7 2004

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Binding energy
binding energy
Ground state
interactions
expansion
ground state
thermodynamic equilibrium
laser induced fluorescence
partitions
Fluorescence
Pumps
Spectroscopy
Thermodynamics
pumps
Color
color
Lasers
probes
high resolution
estimates

ASJC Scopus subject areas

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

Cite this

A combined experimental/theoretical investigation of the He + ICl interactions : Determination of the binding energies of the T-shaped and linear He⋯I35Cl(X,ν″ = 0) conformers. / Boucher, David S.; Darr, Joshua P.; Bradke, Matthew D.; Loomis, Richard A.; McCoy, Anne B.

In: Physical Chemistry Chemical Physics, Vol. 6, No. 23, 07.12.2004, p. 5275-5282.

Research output: Contribution to journalArticle

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