Advanced

Study of substituent effects for aliphatic CH3-X compounds by resonant Auger spectroscopy

Travnikova, Oksana; Svensson, Svante; Céolin, Denis LU ; Bao, Zhuo and Piancastelli, Maria Novella (2009) In Physical Chemistry Chemical Physics 11(5). p.826-833
Abstract
In this study linear free energy relationships (LFER) are applied to the relaxation of core-excited states in aliphatic CH3X compounds. There are at least two valence orbitals involved in Auger decay following C-CH3 1s -> sigma*(C-X) excitation, which may as well be localized on the substituents in this series. Therefore, the observed property cannot be strictly attached to the so-called reaction center. The behavior of substituent constants in the description of core-hole processes in aliphatic compounds is also checked on C1s ionization potentials for the extended series of substituted methanes. The role of the inductive effect for both resonant Auger kinetic energies (E-k) and C1s binding energies (E-b(core)) is very important. C-CH3... (More)
In this study linear free energy relationships (LFER) are applied to the relaxation of core-excited states in aliphatic CH3X compounds. There are at least two valence orbitals involved in Auger decay following C-CH3 1s -> sigma*(C-X) excitation, which may as well be localized on the substituents in this series. Therefore, the observed property cannot be strictly attached to the so-called reaction center. The behavior of substituent constants in the description of core-hole processes in aliphatic compounds is also checked on C1s ionization potentials for the extended series of substituted methanes. The role of the inductive effect for both resonant Auger kinetic energies (E-k) and C1s binding energies (E-b(core)) is very important. C-CH3 1s -> sigma*(C-X) excitation energies do not show any signi. cant correlations with inductive substituent constants. On the contrary, Taft's inductive parameters alone give good correlations for Ek. A simple model with 'Z + 1' approximation is developed to describe Ek and explain the observed correlations: E-k = E-b(core) - (E-b(v(Z)) + Eea(Z+1)+), where E-b(v(Z)) is the valence ionization potential for CH3X and Eea(Z+1)+ is the electron affinity for [NH3X](+). (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
11
issue
5
pages
826 - 833
publisher
Royal Society of Chemistry
external identifiers
  • wos:000262649300009
  • scopus:58649084110
ISSN
1463-9084
DOI
10.1039/b805912h
language
English
LU publication?
yes
id
58d0b494-3bdb-43cd-81a7-2cee4618d7a8 (old id 1312433)
date added to LUP
2009-03-13 14:01:54
date last changed
2017-01-01 05:36:45
@article{58d0b494-3bdb-43cd-81a7-2cee4618d7a8,
  abstract     = {In this study linear free energy relationships (LFER) are applied to the relaxation of core-excited states in aliphatic CH3X compounds. There are at least two valence orbitals involved in Auger decay following C-CH3 1s -> sigma*(C-X) excitation, which may as well be localized on the substituents in this series. Therefore, the observed property cannot be strictly attached to the so-called reaction center. The behavior of substituent constants in the description of core-hole processes in aliphatic compounds is also checked on C1s ionization potentials for the extended series of substituted methanes. The role of the inductive effect for both resonant Auger kinetic energies (E-k) and C1s binding energies (E-b(core)) is very important. C-CH3 1s -> sigma*(C-X) excitation energies do not show any signi. cant correlations with inductive substituent constants. On the contrary, Taft's inductive parameters alone give good correlations for Ek. A simple model with 'Z + 1' approximation is developed to describe Ek and explain the observed correlations: E-k = E-b(core) - (E-b(v(Z)) + Eea(Z+1)+), where E-b(v(Z)) is the valence ionization potential for CH3X and Eea(Z+1)+ is the electron affinity for [NH3X](+).},
  author       = {Travnikova, Oksana and Svensson, Svante and Céolin, Denis and Bao, Zhuo and Piancastelli, Maria Novella},
  issn         = {1463-9084},
  language     = {eng},
  number       = {5},
  pages        = {826--833},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Study of substituent effects for aliphatic CH3-X compounds by resonant Auger spectroscopy},
  url          = {http://dx.doi.org/10.1039/b805912h},
  volume       = {11},
  year         = {2009},
}