Molecular structure and molecular vibrations of 1,3,5,7,-tetramethyl-2,4,6,8,9,10-hexathiaadamantane

Gergely Szász, Attila Kovács, I. Hargittai, Ingyu Jeon, Glen P. Miller

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Abstract

The molecular structure and vibrations of 1,3,5,7,-tetramethyl-2,4,6,8,9,10-hexathiaadamantane have been determined by a joint computational, gas-phase electron diffraction, and spectroscopic investigation. The geometry and harmonic force field of the molecule was calculated at the Becke3-Lee-Yang-Parr/6-31G* level. Vibrational analysis was performed using FT-IR and FT-Raman spectra recorded in the 4000-150 cm-1 range and utilizing Pulay's DFT-based scaled quantum mechanical (SQM) method (DFT: density-functional theory). This SQM method was extended to molecules containing C-S structural motifs. The joint computational and electron diffraction analysis resulted in an equilibrium geometry of Td symmetry characterized by staggered orientation of the methyl groups with respect to their adjacent C-S bonds. The electron diffraction study yielded the following bond lengths (rg) and bond angles (with estimated total errors): C-S, 1.820 ± 0.004 Å; C-C, 1.536 ± 0.004 Å; C-H, 1.119 ± 0.005 Å; C-S-C, 102.2 ± 0.2°; H-C-H, 109.9 ± 0.7°. The barrier to methyl rotation was computed to be 17 kJ/mol in good agreement with that estimated from the average methyl torsion (with respect to the staggered form) of 10 ± 3° from the electron diffraction analysis.

Original languageEnglish
Pages (from-to)484-489
Number of pages6
JournalJournal of Physical Chemistry A
Volume102
Issue number2
Publication statusPublished - Jan 8 1998

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Molecular vibrations
Electron diffraction
Molecular structure
molecular structure
electron diffraction
vibration
Discrete Fourier transforms
Molecules
Geometry
Bond length
geometry
Torsional stress
field theory (physics)
torsion
Density functional theory
Raman scattering
molecules
Gases
Raman spectra
vapor phases

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Molecular structure and molecular vibrations of 1,3,5,7,-tetramethyl-2,4,6,8,9,10-hexathiaadamantane. / Szász, Gergely; Kovács, Attila; Hargittai, I.; Jeon, Ingyu; Miller, Glen P.

In: Journal of Physical Chemistry A, Vol. 102, No. 2, 08.01.1998, p. 484-489.

Research output: Contribution to journalArticle

Szász, Gergely ; Kovács, Attila ; Hargittai, I. ; Jeon, Ingyu ; Miller, Glen P. / Molecular structure and molecular vibrations of 1,3,5,7,-tetramethyl-2,4,6,8,9,10-hexathiaadamantane. In: Journal of Physical Chemistry A. 1998 ; Vol. 102, No. 2. pp. 484-489.
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abstract = "The molecular structure and vibrations of 1,3,5,7,-tetramethyl-2,4,6,8,9,10-hexathiaadamantane have been determined by a joint computational, gas-phase electron diffraction, and spectroscopic investigation. The geometry and harmonic force field of the molecule was calculated at the Becke3-Lee-Yang-Parr/6-31G* level. Vibrational analysis was performed using FT-IR and FT-Raman spectra recorded in the 4000-150 cm-1 range and utilizing Pulay's DFT-based scaled quantum mechanical (SQM) method (DFT: density-functional theory). This SQM method was extended to molecules containing C-S structural motifs. The joint computational and electron diffraction analysis resulted in an equilibrium geometry of Td symmetry characterized by staggered orientation of the methyl groups with respect to their adjacent C-S bonds. The electron diffraction study yielded the following bond lengths (rg) and bond angles (with estimated total errors): C-S, 1.820 ± 0.004 {\AA}; C-C, 1.536 ± 0.004 {\AA}; C-H, 1.119 ± 0.005 {\AA}; C-S-C, 102.2 ± 0.2°; H-C-H, 109.9 ± 0.7°. The barrier to methyl rotation was computed to be 17 kJ/mol in good agreement with that estimated from the average methyl torsion (with respect to the staggered form) of 10 ± 3° from the electron diffraction analysis.",
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