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

Coffin, James M.; Hamilton, Tracy P.; Pulay, Péter; Hargittai, István

doi:10.1021/ic00321a012

Cited by 31 publications

(11 citation statements)

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“…A computational study on the dimers of silicon and germanium dichlorides and dibromides 235 at the HF level supported the C 2v -and C 2h -symmetry geometries as the minimum energy geometry (see Figure 16 (2 and 3)). …”

Section: Dimersmentioning

confidence: 84%

“…Since the ED data could not be interpreted by the monomer alone, 221 the possible presence of dimers and excited-state monomers has been invoked. Later computations 235,236,239 as well as a most recent reanalysis of the experimental data, augmented with computation, 245 excluded the presence of excited-state molecules. The difficulties of interpretation may have been caused by a contamination of FeBr 2 being formed as a product of a The experimental bond angles for the larger halides are not quoted, since due to the very poorly determined nonbonded distances they do not appear to be reliable (see also Figure 22 …”

Section: Dimersmentioning

confidence: 99%

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Molecular Structure of Metal Halides

2000

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Section: Dimersmentioning

confidence: 84%

Section: Dimersmentioning

confidence: 99%

Molecular Structure of Metal Halides

2000

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“…To our knowledge the isomerizations between the chlorinated silylsilylenes and disilenes have not previously been studied theoretically or experimentally. Theoretical investigations of the thermochemistry and reactions of the silanes and halosilanes through 1992 were reviewed by Gordon et al 12 Several studies [13][14][15][16][17] have suggested that, in addition to dimerizing to form disilanes, silylenes can dimerize to form dibridged structures such as the one illustrated in Figure 1b. For Si 2 H 4 , Trinquier 15 predicted the dibridged structure to be about 22.5 kcal/mol above the disilene.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Molecular Orbital Study of the Thermochemistry and Reactions of the Chlorinated Disilenes and Their Isomers (Si₂H_nCl_4-n)

Swihart

Carr

1998

J. Phys. Chem. A

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Structures, vibrational frequencies, and energies for the chlorinated disilenes, their dibridged isomers, and the transition states connecting the chlorinated disilenes to the corresponding silylsilylenes are presented. Geometries and frequencies were obtained at the MP2/6-31G(d,p) level, and energetics were calculated at the G2, G2(MP2), MP4/6-31+G(2df,p), and/or MP2/6-31+G(2df,p) levels of theory, depending on the number of chlorine atoms in the molecule. The silylsilylene isomer with the structure H n Cl 3-n SiSiCl was found to be lowest in energy for all of the chlorinated compounds. The dibridged structures are all significantly higher in energy than the silylsilylene and disilene structures. Barriers for isomerization by H transfer and Cl transfer ranged from 5 to 18 kcal/mol and 9 to 23 kcal/mol above the disilene, respectively. Energies along paths for decomposition of the chlorinated disilenes to pairs of silylenes are presented, confirming that the reverse reactions are barrierless. Finally, energetics of various decomposition products of the Si 2 H n Cl 4-n compounds are considered. It is shown that for the species with two or more chlorines, decomposition to a pair of silylenes should be the dominant reaction path based on the energetics of competing paths. The isomerization barriers are much smaller than decomposition barriers, so the isomerization reactions will be fast compared to decomposition.

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“…For the main isotopic species the theoretical results for the molecular geometries, the spectroscopic constants, and the full quartic force fields are calculated. They are compared with the corresponding experimental or empirical data [6,9,17,25] whenever these are [27].…”

Section: Resultsmentioning

confidence: 99%

Ab initio Study of Anharmonic Force Field and Spectroscopic Constants for Germanium Dichloride

Pang

Sun

Zhao

et al. 2016

Chinese Journal of Chemical Physics

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Ab initio study of the equilibrium structure, spectroscopy constants, and anharmonic force field for several isotopomers of germanium dichloride (70 GeCl 2 , 72 GeCl 2 , and 76 GeCl 2) have been carried out at the MP2 and CCSD(T) levels of theory using cc-pVTZ basis set. The calculated geometries, rotational constants, vibration-rotation interaction constants, harmonic frequencies, anharmonic constants, quartic and sextic centrifugal distortion constants, cubic and quartic force constants are compared with experimental data. For small mass differences of the Ge isotopes, the isotopic effects for germanium dichloride are much weaker. The agreements are satisfactory for these two methods, but the deviations of CCSD(T) results are slightly larger than that of MP2, because of CCSD(T)'s inadequate treatment of electron correlation in hypervalent Cl atom.

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

Cited by 31 publications

References 0 publications

Molecular Structure of Metal Halides

Molecular Structure of Metal Halides

Ab Initio Molecular Orbital Study of the Thermochemistry and Reactions of the Chlorinated Disilenes and Their Isomers (Si₂H_nCl_4-n)

Ab initio Study of Anharmonic Force Field and Spectroscopic Constants for Germanium Dichloride

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

Cited by 31 publications

References 0 publications

Molecular Structure of Metal Halides

Molecular Structure of Metal Halides

Ab Initio Molecular Orbital Study of the Thermochemistry and Reactions of the Chlorinated Disilenes and Their Isomers (Si2HnCl4-n)

Ab initio Study of Anharmonic Force Field and Spectroscopic Constants for Germanium Dichloride

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Ab Initio Molecular Orbital Study of the Thermochemistry and Reactions of the Chlorinated Disilenes and Their Isomers (Si₂H_nCl_4-n)