Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride

Joshua Paul Darr, Andrew C. Crowther, Richard A. Loomis, Sara E. Ray, Anne B. McCoy

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Abstract

The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,/p-H2...I35,37Cl(X,v″:= 0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v, symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D 0&Prime = 186.4(3) cm-1 versus 82.8(3) ≤ D 0″ ≤ 89.6(3) cm-1. Complexes containing the 0-H2(Z=1) species are more strongly bound than those with P-H 2(Z=0). The electronically excited o,p-H2⋯I 35Cl(A,v́) and O,p-H2⋯I35,37C1(B, v́) complexes are found to have preferred asymmetric structures with binding energies bracketed between 73.7-80.5 and 69.5-76.3 cm-1 for o-H2⋯ I35Cl(A,v́=23) and o-H 2⋯I35Cl(B,v́=3), respectively. Calculations of the H2-I35C1(B,v́=3) intermolecular vibrational energies and probability amplitudes undertaken using a scaled He + ICl(B,v́=3) potential enable us to make tentative assignments of the excited-state levels experimentally accessed.

Original languageEnglish (US)
Pages (from-to)13387-13396
Number of pages10
JournalJournal of Physical Chemistry A
Volume111
Issue number51
DOIs
StatePublished - Dec 27 2007

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iodine
Hydrogen
Atoms
hydrogen
atoms
Molecules
Molecular interactions
interactions
Binding energy
Excited states
Iodine
laser induced fluorescence
molecules
binding energy
Fluorescence
Spectroscopy
Geometry
Lasers
symmetry
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride. / Darr, Joshua Paul; Crowther, Andrew C.; Loomis, Richard A.; Ray, Sara E.; McCoy, Anne B.

In: Journal of Physical Chemistry A, Vol. 111, No. 51, 27.12.2007, p. 13387-13396.

Research output: Contribution to journalArticle

Darr, Joshua Paul ; Crowther, Andrew C. ; Loomis, Richard A. ; Ray, Sara E. ; McCoy, Anne B. / Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 51. pp. 13387-13396.
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abstract = "The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,/p-H2...I35,37Cl(X,v″:= 0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v, symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D 0&Prime = 186.4(3) cm-1 versus 82.8(3) ≤ D 0″ ≤ 89.6(3) cm-1. Complexes containing the 0-H2(Z=1) species are more strongly bound than those with P-H 2(Z=0). The electronically excited o,p-H2⋯I 35Cl(A,v́) and O,p-H2⋯I35,37C1(B, v́) complexes are found to have preferred asymmetric structures with binding energies bracketed between 73.7-80.5 and 69.5-76.3 cm-1 for o-H2⋯ I35Cl(A,v́=23) and o-H 2⋯I35Cl(B,v́=3), respectively. Calculations of the H2-I35C1(B,v́=3) intermolecular vibrational energies and probability amplitudes undertaken using a scaled He + ICl(B,v́=3) potential enable us to make tentative assignments of the excited-state levels experimentally accessed.",
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T1 - Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride

AU - Darr, Joshua Paul

AU - Crowther, Andrew C.

AU - Loomis, Richard A.

AU - Ray, Sara E.

AU - McCoy, Anne B.

PY - 2007/12/27

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N2 - The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,/p-H2...I35,37Cl(X,v″:= 0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v, symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D 0&Prime = 186.4(3) cm-1 versus 82.8(3) ≤ D 0″ ≤ 89.6(3) cm-1. Complexes containing the 0-H2(Z=1) species are more strongly bound than those with P-H 2(Z=0). The electronically excited o,p-H2⋯I 35Cl(A,v́) and O,p-H2⋯I35,37C1(B, v́) complexes are found to have preferred asymmetric structures with binding energies bracketed between 73.7-80.5 and 69.5-76.3 cm-1 for o-H2⋯ I35Cl(A,v́=23) and o-H 2⋯I35Cl(B,v́=3), respectively. Calculations of the H2-I35C1(B,v́=3) intermolecular vibrational energies and probability amplitudes undertaken using a scaled He + ICl(B,v́=3) potential enable us to make tentative assignments of the excited-state levels experimentally accessed.

AB - The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,/p-H2...I35,37Cl(X,v″:= 0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v, symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D 0&Prime = 186.4(3) cm-1 versus 82.8(3) ≤ D 0″ ≤ 89.6(3) cm-1. Complexes containing the 0-H2(Z=1) species are more strongly bound than those with P-H 2(Z=0). The electronically excited o,p-H2⋯I 35Cl(A,v́) and O,p-H2⋯I35,37C1(B, v́) complexes are found to have preferred asymmetric structures with binding energies bracketed between 73.7-80.5 and 69.5-76.3 cm-1 for o-H2⋯ I35Cl(A,v́=23) and o-H 2⋯I35Cl(B,v́=3), respectively. Calculations of the H2-I35C1(B,v́=3) intermolecular vibrational energies and probability amplitudes undertaken using a scaled He + ICl(B,v́=3) potential enable us to make tentative assignments of the excited-state levels experimentally accessed.

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