Study of substituent effects for aliphatic CH3–X compounds by resonant Auger spectroscopy
文献信息
Oksana Travnikova, Svante Svensson, Denis Céolin, Zhuo Bao, Maria Novella Piancastelli
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 CCH31s →σ*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 (Ek) and C1s binding energies (Ecoreb) is very important. CCH31s →σ*C–X excitation energies do not show any significant 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:Ek = Ecoreb− (Ev(Z)b + Eea(Z+1)+),where Ebv(Z) is the valence ionization potential for CH3X and Eea(Z+1)+ is the electron affinity for [NH3X]+.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














