Abstract
We report discrete-variational method Hartree-Fock-Slater (HFS) calculations on the title compounds. For a self-consistent potential based upon a Mulliken superposition of spherical charge densities (the self-consistent-charge scheme) the orbital energetics exhibit substantial disagreement with experiment; inclusion of more radial structure (and, less effectively, of p waves) in the self-consistent potential produces excellent experimental agreement, and permits us to assign the lowest optical excited state as an eu π-type state with some Si d-function character. This is essentially in agreement with an early experimental assignment of Gilman. Electron delocalization in silane oligomers is rationalized on the basis of empty orbital energetics and spatial structure. For proper description of diffuse molecular states and optical excitations, we emphasize the necessity of utilizing a sufficiently flexible representation of the molecular potential.
| Original language | English |
|---|---|
| Pages (from-to) | 21-35 |
| Number of pages | 15 |
| Journal | Chemical Physics |
| Volume | 62 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Nov 1 1981 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Spectroscopy
- Atomic and Molecular Physics, and Optics
Cite this
Intramolecular electron localization and local-density calculations on silicon-containing molecules : Tetramethylsilane and hexamethyldisilane. / Berkovitch-yellin, Z.; Ellis, D. E.; Ratner, Mark A.
In: Chemical Physics, Vol. 62, No. 1-2, 01.11.1981, p. 21-35.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Intramolecular electron localization and local-density calculations on silicon-containing molecules
T2 - Tetramethylsilane and hexamethyldisilane
AU - Berkovitch-yellin, Z.
AU - Ellis, D. E.
AU - Ratner, Mark A
PY - 1981/11/1
Y1 - 1981/11/1
N2 - We report discrete-variational method Hartree-Fock-Slater (HFS) calculations on the title compounds. For a self-consistent potential based upon a Mulliken superposition of spherical charge densities (the self-consistent-charge scheme) the orbital energetics exhibit substantial disagreement with experiment; inclusion of more radial structure (and, less effectively, of p waves) in the self-consistent potential produces excellent experimental agreement, and permits us to assign the lowest optical excited state as an eu π-type state with some Si d-function character. This is essentially in agreement with an early experimental assignment of Gilman. Electron delocalization in silane oligomers is rationalized on the basis of empty orbital energetics and spatial structure. For proper description of diffuse molecular states and optical excitations, we emphasize the necessity of utilizing a sufficiently flexible representation of the molecular potential.
AB - We report discrete-variational method Hartree-Fock-Slater (HFS) calculations on the title compounds. For a self-consistent potential based upon a Mulliken superposition of spherical charge densities (the self-consistent-charge scheme) the orbital energetics exhibit substantial disagreement with experiment; inclusion of more radial structure (and, less effectively, of p waves) in the self-consistent potential produces excellent experimental agreement, and permits us to assign the lowest optical excited state as an eu π-type state with some Si d-function character. This is essentially in agreement with an early experimental assignment of Gilman. Electron delocalization in silane oligomers is rationalized on the basis of empty orbital energetics and spatial structure. For proper description of diffuse molecular states and optical excitations, we emphasize the necessity of utilizing a sufficiently flexible representation of the molecular potential.
UR - http://www.scopus.com/inward/record.url?scp=0005351678&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0005351678&partnerID=8YFLogxK
U2 - 10.1016/0301-0104(81)80183-8
DO - 10.1016/0301-0104(81)80183-8
M3 - Article
AN - SCOPUS:0005351678
VL - 62
SP - 21
EP - 35
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 1-2
ER -