Probing the dependence of long-range, four-atom interactions on intermolecular orientation

3. hydrogen and iodine

Joshua Paul Darr, Richard A. Loomis, Sara E. Ray-Helmus, Anne B. McCoy

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Two-laser, action spectroscopy experiments have been performed in the I2B-X, ν′-0 spectral region on H 2•••I2 and D2••• I2 complexes to investigate the dependence of the H 2/D2 + I2 intermolecular interactions on orientation. The spectra contain features associated with at least two different conformers of the ground-state H2/D2••• I2(X,ν′′ = 0) complexes; one conformer has a preferred T-shaped geometry with the H2/D2 moiety localized in a potential minimum that is orthogonal to the I-I bond axis, and the second conformer has a linear geometry with the H2/D2 moiety positioned in minima at either end of the I2 molecule, along the bond axis. Those features associated with complexes containing para-H2(j = 0), ortho-H2(j = 1), ortho-D2(j = 0), and para-D 2(j = 1) are also assigned. The linear conformers are found to be more strongly bound than the T-shaped conformers with binding energies of 118.9(1.9) cm-1 versus 91.3-93.3 cm-1 for the ortho-H 2•••I2 complexes and 144.2(2.1) cm -1 versus 107.9 cm-1 for the para-D2• ••I2 complexes, respectively. Electronic structure calculations of the complexes containing ICl and I2 with H 2, He, Ne, and Ar were performed to reveal the nature of the interactions and to shed insight into the origins of the different binding energies. The most stable minima in the H2/D2 + I 2(B,ν′) excited-state potentials have T-shaped geometries. Calculated energies and probability amplitudes of the excited-state levels provide insight into the different excited-state intermolecular vibrational levels accessed by transitions of the two ground-state conformers.

Original languageEnglish (US)
Pages (from-to)7368-7377
Number of pages10
JournalJournal of Physical Chemistry A
Volume115
Issue number25
DOIs
StatePublished - Jun 30 2011

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Excited states
Iodine
iodine
Hydrogen
Binding energy
Atoms
Ground state
Geometry
hydrogen
geometry
binding energy
excitation
atoms
ground state
interactions
Electron transitions
Electronic structure
Spectroscopy
electronic structure
Molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Probing the dependence of long-range, four-atom interactions on intermolecular orientation : 3. hydrogen and iodine. / Darr, Joshua Paul; Loomis, Richard A.; Ray-Helmus, Sara E.; McCoy, Anne B.

In: Journal of Physical Chemistry A, Vol. 115, No. 25, 30.06.2011, p. 7368-7377.

Research output: Contribution to journalArticle

Darr, Joshua Paul ; Loomis, Richard A. ; Ray-Helmus, Sara E. ; McCoy, Anne B. / Probing the dependence of long-range, four-atom interactions on intermolecular orientation : 3. hydrogen and iodine. In: Journal of Physical Chemistry A. 2011 ; Vol. 115, No. 25. pp. 7368-7377.
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abstract = "Two-laser, action spectroscopy experiments have been performed in the I2B-X, ν′-0 spectral region on H 2•••I2 and D2••• I2 complexes to investigate the dependence of the H 2/D2 + I2 intermolecular interactions on orientation. The spectra contain features associated with at least two different conformers of the ground-state H2/D2••• I2(X,ν′′ = 0) complexes; one conformer has a preferred T-shaped geometry with the H2/D2 moiety localized in a potential minimum that is orthogonal to the I-I bond axis, and the second conformer has a linear geometry with the H2/D2 moiety positioned in minima at either end of the I2 molecule, along the bond axis. Those features associated with complexes containing para-H2(j = 0), ortho-H2(j = 1), ortho-D2(j = 0), and para-D 2(j = 1) are also assigned. The linear conformers are found to be more strongly bound than the T-shaped conformers with binding energies of 118.9(1.9) cm-1 versus 91.3-93.3 cm-1 for the ortho-H 2•••I2 complexes and 144.2(2.1) cm -1 versus 107.9 cm-1 for the para-D2• ••I2 complexes, respectively. Electronic structure calculations of the complexes containing ICl and I2 with H 2, He, Ne, and Ar were performed to reveal the nature of the interactions and to shed insight into the origins of the different binding energies. The most stable minima in the H2/D2 + I 2(B,ν′) excited-state potentials have T-shaped geometries. Calculated energies and probability amplitudes of the excited-state levels provide insight into the different excited-state intermolecular vibrational levels accessed by transitions of the two ground-state conformers.",
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