Molecular geometry of monomeric and dimeric yttrium trichloride from gas-phase electron diffraction and quantum chemical calculations

Balázs Réffy, Colin J. Marsden, M. Hargittai

Research output: Contribution to journalArticle

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Abstract

The molecular geometry of yttrium trichloride has been determined by high-temperature gas-phase electron diffraction. The vapor phase consisted of about 87% monomeric and 13% dimeric species. High-level quantum chemical calculations have also been carried out for both the monomer and dimer of yttrium trichloride, and their geometries, harmonic force fields, and vibrational frequencies have been determined. The monomer YCl3 molecule was found to be planar (D3h symmetry) both by experiment and by computation. The bond length of YCl3 from electron diffraction is 2.450(7) (rg) or 2.422(12) (re) Å. It proved remarkably difficult to obtain a converged theoretical prediction for the bond length; large polarization bases are needed, and the published bases accompanying the pseudopotentials used appear to be overcontracted. The SCF method predicts bonds that are too long by some 0.043 Å, whereas the B3LYP method overestimates by about 0.03 Å. The B3PW91 prediction is almost within the experimental uncertainty for re. Among the traditional correlated methods, the MP2 distance with an infinitely large basis is probably indistinguishable from the experimental value, given the combined uncertainties, whereas the estimated CCSD(T) result of 2.423(10) Å is astonishingly close to the experimental result. The out-of-plane bending motion for YCl3 is noticeably anharmonic, with the result that straightforward quantum predictions of its frequency are lower than the value observed in the gas phase at high temperature.

Original languageEnglish
Pages (from-to)1840-1849
Number of pages10
JournalJournal of Physical Chemistry A
Volume107
Issue number11
DOIs
Publication statusPublished - Mar 20 2003

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Yttrium
yttrium
Electron diffraction
electron diffraction
Gases
chlorides
Bond length
vapor phases
Geometry
monomers
geometry
predictions
Monomers
high temperature gases
Vibrational spectra
Dimers
field theory (physics)
pseudopotentials
self consistent fields
Vapors

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Molecular geometry of monomeric and dimeric yttrium trichloride from gas-phase electron diffraction and quantum chemical calculations. / Réffy, Balázs; Marsden, Colin J.; Hargittai, M.

In: Journal of Physical Chemistry A, Vol. 107, No. 11, 20.03.2003, p. 1840-1849.

Research output: Contribution to journalArticle

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abstract = "The molecular geometry of yttrium trichloride has been determined by high-temperature gas-phase electron diffraction. The vapor phase consisted of about 87{\%} monomeric and 13{\%} dimeric species. High-level quantum chemical calculations have also been carried out for both the monomer and dimer of yttrium trichloride, and their geometries, harmonic force fields, and vibrational frequencies have been determined. The monomer YCl3 molecule was found to be planar (D3h symmetry) both by experiment and by computation. The bond length of YCl3 from electron diffraction is 2.450(7) (rg) or 2.422(12) (re) {\AA}. It proved remarkably difficult to obtain a converged theoretical prediction for the bond length; large polarization bases are needed, and the published bases accompanying the pseudopotentials used appear to be overcontracted. The SCF method predicts bonds that are too long by some 0.043 {\AA}, whereas the B3LYP method overestimates by about 0.03 {\AA}. The B3PW91 prediction is almost within the experimental uncertainty for re. Among the traditional correlated methods, the MP2 distance with an infinitely large basis is probably indistinguishable from the experimental value, given the combined uncertainties, whereas the estimated CCSD(T) result of 2.423(10) {\AA} is astonishingly close to the experimental result. The out-of-plane bending motion for YCl3 is noticeably anharmonic, with the result that straightforward quantum predictions of its frequency are lower than the value observed in the gas phase at high temperature.",
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N2 - The molecular geometry of yttrium trichloride has been determined by high-temperature gas-phase electron diffraction. The vapor phase consisted of about 87% monomeric and 13% dimeric species. High-level quantum chemical calculations have also been carried out for both the monomer and dimer of yttrium trichloride, and their geometries, harmonic force fields, and vibrational frequencies have been determined. The monomer YCl3 molecule was found to be planar (D3h symmetry) both by experiment and by computation. The bond length of YCl3 from electron diffraction is 2.450(7) (rg) or 2.422(12) (re) Å. It proved remarkably difficult to obtain a converged theoretical prediction for the bond length; large polarization bases are needed, and the published bases accompanying the pseudopotentials used appear to be overcontracted. The SCF method predicts bonds that are too long by some 0.043 Å, whereas the B3LYP method overestimates by about 0.03 Å. The B3PW91 prediction is almost within the experimental uncertainty for re. Among the traditional correlated methods, the MP2 distance with an infinitely large basis is probably indistinguishable from the experimental value, given the combined uncertainties, whereas the estimated CCSD(T) result of 2.423(10) Å is astonishingly close to the experimental result. The out-of-plane bending motion for YCl3 is noticeably anharmonic, with the result that straightforward quantum predictions of its frequency are lower than the value observed in the gas phase at high temperature.

AB - The molecular geometry of yttrium trichloride has been determined by high-temperature gas-phase electron diffraction. The vapor phase consisted of about 87% monomeric and 13% dimeric species. High-level quantum chemical calculations have also been carried out for both the monomer and dimer of yttrium trichloride, and their geometries, harmonic force fields, and vibrational frequencies have been determined. The monomer YCl3 molecule was found to be planar (D3h symmetry) both by experiment and by computation. The bond length of YCl3 from electron diffraction is 2.450(7) (rg) or 2.422(12) (re) Å. It proved remarkably difficult to obtain a converged theoretical prediction for the bond length; large polarization bases are needed, and the published bases accompanying the pseudopotentials used appear to be overcontracted. The SCF method predicts bonds that are too long by some 0.043 Å, whereas the B3LYP method overestimates by about 0.03 Å. The B3PW91 prediction is almost within the experimental uncertainty for re. Among the traditional correlated methods, the MP2 distance with an infinitely large basis is probably indistinguishable from the experimental value, given the combined uncertainties, whereas the estimated CCSD(T) result of 2.423(10) Å is astonishingly close to the experimental result. The out-of-plane bending motion for YCl3 is noticeably anharmonic, with the result that straightforward quantum predictions of its frequency are lower than the value observed in the gas phase at high temperature.

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