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.
N1 - Funding Information:
Z.B. is grateful for receipt of a Weizmann Fellowship. We thank the Chemistry Division of the National Science Foundation for support of this research, and Bernard Delley for extremely valuable discussions and computational help. The telling and incisive comments from a referee on a previous version were very helpful in deveIoping the fina draft of this manuscript-we are very grateful to him.
Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
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.
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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 -