Structure, spectra, and intramolecular motions of 1,4-bis(trimethylsilyl)-1,3-butadiyne

An electron diffraction study using the results of spectral analysis based on scaled quantum-chemical force field for calculating vibrational effects

M. Traetteberg, L. S. Khaikin, O. E. Grikina, J. F. Liebman, Martin Hulce

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Abstract

The molecular structure of 1,4-bis(trimethylsilyl)-1,3-butadiyne has been studied by the gas electron diffraction method and by ab initio calculations at the RHF and MP2 levels. A scaled quantum-chemical force field was used to interpret the vibrational spectra. The root-mean-square vibrational amplitudes and harmonic shrinkage corrections were calculated taking into account non-linear relations between Cartesian and internal vibrational co-ordinates at the level of first-order perturbation theory (h1) and with the use of the traditional scheme (h0). The total energies of the D3d and D3h conformers differ by about 1 cal mol-1 (0.4 cm-1) which implies virtually free internal rotation. It has been shown that the flexibility of the linear fragment in (CH3)3Si-C≡C-C≡C-Si (CH3)3 has increased considerably compared to that in (CH3)3Si-C≡C-Si(CH3)3.

Original languageEnglish
Pages (from-to)295-313
Number of pages19
JournalJournal of Molecular Structure
Volume559
Issue number1-3
DOIs
StatePublished - Jan 7 2001

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Vibrational spectra
Molecular Structure
Electron diffraction
Spectrum analysis
Molecular structure
field theory (physics)
spectrum analysis
electron diffraction
Gases
Electrons
shrinkage
vibrational spectra
flexibility
molecular structure
perturbation theory
fragments
harmonics
gases
energy

All Science Journal Classification (ASJC) codes

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Structure, spectra, and intramolecular motions of 1,4-bis(trimethylsilyl)-1,3-butadiyne: An electron diffraction study using the results of spectral analysis based on scaled quantum-chemical force field for calculating vibrational effects",
abstract = "The molecular structure of 1,4-bis(trimethylsilyl)-1,3-butadiyne has been studied by the gas electron diffraction method and by ab initio calculations at the RHF and MP2 levels. A scaled quantum-chemical force field was used to interpret the vibrational spectra. The root-mean-square vibrational amplitudes and harmonic shrinkage corrections were calculated taking into account non-linear relations between Cartesian and internal vibrational co-ordinates at the level of first-order perturbation theory (h1) and with the use of the traditional scheme (h0). The total energies of the D3d and D3h conformers differ by about 1 cal mol-1 (0.4 cm-1) which implies virtually free internal rotation. It has been shown that the flexibility of the linear fragment in (CH3)3Si-C≡C-C≡C-Si (CH3)3 has increased considerably compared to that in (CH3)3Si-C≡C-Si(CH3)3.",
author = "M. Traetteberg and Khaikin, {L. S.} and Grikina, {O. E.} and Liebman, {J. F.} and Martin Hulce",
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T1 - Structure, spectra, and intramolecular motions of 1,4-bis(trimethylsilyl)-1,3-butadiyne

T2 - An electron diffraction study using the results of spectral analysis based on scaled quantum-chemical force field for calculating vibrational effects

AU - Traetteberg, M.

AU - Khaikin, L. S.

AU - Grikina, O. E.

AU - Liebman, J. F.

AU - Hulce, Martin

PY - 2001/1/7

Y1 - 2001/1/7

N2 - The molecular structure of 1,4-bis(trimethylsilyl)-1,3-butadiyne has been studied by the gas electron diffraction method and by ab initio calculations at the RHF and MP2 levels. A scaled quantum-chemical force field was used to interpret the vibrational spectra. The root-mean-square vibrational amplitudes and harmonic shrinkage corrections were calculated taking into account non-linear relations between Cartesian and internal vibrational co-ordinates at the level of first-order perturbation theory (h1) and with the use of the traditional scheme (h0). The total energies of the D3d and D3h conformers differ by about 1 cal mol-1 (0.4 cm-1) which implies virtually free internal rotation. It has been shown that the flexibility of the linear fragment in (CH3)3Si-C≡C-C≡C-Si (CH3)3 has increased considerably compared to that in (CH3)3Si-C≡C-Si(CH3)3.

AB - The molecular structure of 1,4-bis(trimethylsilyl)-1,3-butadiyne has been studied by the gas electron diffraction method and by ab initio calculations at the RHF and MP2 levels. A scaled quantum-chemical force field was used to interpret the vibrational spectra. The root-mean-square vibrational amplitudes and harmonic shrinkage corrections were calculated taking into account non-linear relations between Cartesian and internal vibrational co-ordinates at the level of first-order perturbation theory (h1) and with the use of the traditional scheme (h0). The total energies of the D3d and D3h conformers differ by about 1 cal mol-1 (0.4 cm-1) which implies virtually free internal rotation. It has been shown that the flexibility of the linear fragment in (CH3)3Si-C≡C-C≡C-Si (CH3)3 has increased considerably compared to that in (CH3)3Si-C≡C-Si(CH3)3.

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