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

2. Molecular deuterium and iodine monochloride

Joshua Paul Darr, Richard A. Loomis, Anne B. McCoy

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the D2 ⋯ ICl van der Waals complex for both ortho-D2 (o-D2) and para-D2 (p-D2). As with die analogous H2 ⋯ ICl van der Waals complexes [Darr, J. P.; Crowther, A. C.; Loomis, R. A.; Ray, S. E.; McCoy, A. B. J. Phys. Chem. A 2007, 111, 13387], the C2v conformer with the deuterium molecule localized at the iodine atom end of the dihalogen is significantly more stable than the asymmetric conformer that has the deuterium positioned orthogonally to the ICl bond axis, D0″ = 223.9(2.4) versus 97.3(8)-103.9(3) cm-1 for p-D2⋯I 35CI(X,v″ = 0). For both conformers, complexes containing p-D2 are found to be more strongly bound than those with o-D 2. The electronically excited D2⋯ICl(A,v′) and D2⋯ICl(B,v′) complexes are found to have equilibrium geometries that are nearly the same as those of the ground-state asymmetric structures. Calculated D2⋯ICl(B,v′=3) energies and probability amplitudes obtained using a simple scaled He + ICl(B,v′=3) potential provide clues to the nature of the different excited-state levels accessed.

Original languageEnglish (US)
Pages (from-to)9494-9502
Number of pages9
JournalJournal of Physical Chemistry A
Volume112
Issue number39
DOIs
StatePublished - Oct 2 2008

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Deuterium
iodine
deuterium
Atoms
Excited states
Iodine
laser induced fluorescence
Ground state
atoms
rays
Fluorescence
interactions
Spectroscopy
Molecules
ground state
Geometry
Lasers
geometry
spectroscopy
excitation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Probing the dependence of long-range, four-atom interactions on intermolecular orientation : 2. Molecular deuterium and iodine monochloride. / Darr, Joshua Paul; Loomis, Richard A.; McCoy, Anne B.

In: Journal of Physical Chemistry A, Vol. 112, No. 39, 02.10.2008, p. 9494-9502.

Research output: Contribution to journalArticle

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abstract = "Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the D2 ⋯ ICl van der Waals complex for both ortho-D2 (o-D2) and para-D2 (p-D2). As with die analogous H2 ⋯ ICl van der Waals complexes [Darr, J. P.; Crowther, A. C.; Loomis, R. A.; Ray, S. E.; McCoy, A. B. J. Phys. Chem. A 2007, 111, 13387], the C2v conformer with the deuterium molecule localized at the iodine atom end of the dihalogen is significantly more stable than the asymmetric conformer that has the deuterium positioned orthogonally to the ICl bond axis, D0″ = 223.9(2.4) versus 97.3(8)-103.9(3) cm-1 for p-D2⋯I 35CI(X,v″ = 0). For both conformers, complexes containing p-D2 are found to be more strongly bound than those with o-D 2. The electronically excited D2⋯ICl(A,v′) and D2⋯ICl(B,v′) complexes are found to have equilibrium geometries that are nearly the same as those of the ground-state asymmetric structures. Calculated D2⋯ICl(B,v′=3) energies and probability amplitudes obtained using a simple scaled He + ICl(B,v′=3) potential provide clues to the nature of the different excited-state levels accessed.",
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