Study of substituent effects for aliphatic CH3-X compounds by resonant Auger spectroscopy
(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:
https://lup.lub.lu.se/record/1312433
- author
- Travnikova, Oksana ; Svensson, Svante ; Céolin, Denis LU ; Bao, Zhuo and Piancastelli, Maria Novella
- organization
- publishing date
- 2009
- 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
- pmid:19290329
- 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
- 2016-04-01 13:20:10
- date last changed
- 2025-04-04 14:12:48
@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}},
doi = {{10.1039/b805912h}},
volume = {{11}},
year = {{2009}},
}