Premium
Application of the Stabilized Koopmans’ Theorem to the Temporary Anion States of Chlorosilanes in Long‐Range Corrected Density Functional Theory
Author(s) -
Cheng HsiuYao,
Huang YuShiuan,
Huang PinQi
Publication year - 2014
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201400069
Subject(s) - chemistry , atomic orbital , ion , density functional theory , range (aeronautics) , scaling , resonance (particle physics) , basis set , character (mathematics) , atomic physics , molecular orbital , molecule , computational chemistry , chemical bond , electron , quantum mechanics , physics , geometry , materials science , organic chemistry , mathematics , composite material
The stabilized Koopmans’ theorem (SKT) is very successful in predicting relative vertical electron attachment energies in the Hartree‐Fock theory. It is mainly accomplished by systematically scaling the most diffuse functions in the basis set. Recently, the SKT has been extended to the temporary anion states (TASs) of polyatomic molecules in the long‐range corrected density functional theory. In this paper, this method will be further applied to chlorosilanes for their importance in the chemical processes of the semiconductor industry. Their resonance energies and lifetimes are determined by computing the density of resonance states via SKT. The detailed characteristics of resonance orbitals are then analyzed. It turns out that the lowest unfilled orbitals of chlorosilanes are essentially σ* Si‐Cl in character. Moreover, several TASs with strong Si/Cl “d” character have been identified. These results, definitely, will help us in understanding the peculiar bonding and chemical properties of chlorosilanes.