Structures, energetics, and vibrational frequencies of the silicon and germanium dichlorides and dibromides and their dimers

J. M. Coffin, T. P. Hamilton, P. Pulay, I. Hargittai

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27 Citations (Scopus)

Abstract

The geometries and energies of the ground singlet (1A1) and first excited triplet (3B1) states of SiCl2, SiBr2, GeCl2, and GeBr2 and the ground states of their dimers were determined from ab initio Hartree-Fock calculations, in order to identify the additional component observed in the electron diffraction radial distribution of GeBr2. The results show that the triplet states of these molecules are 140-200 kJ/mol higher in energy than the singlet states and can be thus excluded as the additional component at the experimental temperature. The bridged dimer of GeBr2 is calculated to be weakly bound and is predicted to be the additional component. We have calculated the force constants and fundamental frequencies of the singlet monomers. The latter, after the usual scaling, agree well with the experimental frequencies. A matrix-infrared study of the system could positively identify the dimer as the additional component, and the predicted vibrational fundamental frequencies of Ge2Br4 are given to assist in this identification.

Original languageEnglish
Pages (from-to)4092-4094
Number of pages3
JournalInorganic Chemistry
Volume28
Issue number22
Publication statusPublished - 1989

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Germanium
dibromides
dichlorides
Vibrational spectra
Silicon
Dimers
germanium
dimers
silicon
atomic energy levels
Electron diffraction
Ground state
Monomers
radial distribution
Infrared radiation
Molecules
Geometry
electron diffraction
monomers
scaling

ASJC Scopus subject areas

  • Inorganic Chemistry

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Structures, energetics, and vibrational frequencies of the silicon and germanium dichlorides and dibromides and their dimers. / Coffin, J. M.; Hamilton, T. P.; Pulay, P.; Hargittai, I.

In: Inorganic Chemistry, Vol. 28, No. 22, 1989, p. 4092-4094.

Research output: Contribution to journalArticle

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AU - Hargittai, I.

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AB - The geometries and energies of the ground singlet (1A1) and first excited triplet (3B1) states of SiCl2, SiBr2, GeCl2, and GeBr2 and the ground states of their dimers were determined from ab initio Hartree-Fock calculations, in order to identify the additional component observed in the electron diffraction radial distribution of GeBr2. The results show that the triplet states of these molecules are 140-200 kJ/mol higher in energy than the singlet states and can be thus excluded as the additional component at the experimental temperature. The bridged dimer of GeBr2 is calculated to be weakly bound and is predicted to be the additional component. We have calculated the force constants and fundamental frequencies of the singlet monomers. The latter, after the usual scaling, agree well with the experimental frequencies. A matrix-infrared study of the system could positively identify the dimer as the additional component, and the predicted vibrational fundamental frequencies of Ge2Br4 are given to assist in this identification.

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