Polarization effect in radical cations and H-complexes

Egorochkin, A. N.; Кузнецова, О. В.

doi:10.1134/s1070428002120035

Cited by 2 publications

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“…The σ α values calculated for different X by ab initio quan tum chemical methods 23 are convenient as characteristics of the polarizability effect in correlation analysis. 11-15, 22 The series I-XVIII (see Tables 1-8) are nonclassical . It is difficult to say a priori which electronic effects of substituents X influence the carbon 1s binding energy E b in carbon cen tered radical cations C •+ X 1 X 2 X 3 X 4 , C •+ H 3 SiX 1 X 2 X 3 , C •+ H 3 GeX 1 X 2 X 3 , C 6…”

Section: 22mentioning

confidence: 99%

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Carbon 1s binding energy and substituent effects in C-centered radical cations

et al. 2009

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The carbon 1s binding energies (E b ) measured by X ray photoelectron spectroscopy or obtained from quantum chemical calculations for 18 series of compounds in which the reaction center is the C atom are analyzed. It was established for the first time that E b values in carbon centered radical cations depend on the inductive, resonance, and polarizability effects of sub stituents.Key words: carbon 1s binding energy, inductive effect, conjugation, polarizability effect of substituents.The photoelectron and X ray electron spectroscopies (PES and XES, respectively) are widely used to study the ionization energies E of the electronic levels of molecules (see, for example, Refs 1-10). The gas phase PES and XES are based on the reaction ,where R C BX is a neutral molecule, R C •+ BX is a radical cation, X is substituent, and е -is an electron.The ionization energy E is equal to the total energy difference between the radical cation and the moleculeWithout loss of generality, we consider that the R C BX molecules form reaction series. Each series contains an invariable reaction center R C , the bridge В, and variable substituents X (in the R C X series, there is no bridge be tween R C and X). Detachment of an electron by reaction (1) occurs only from R C . Therefore, the formation of R C •+ BX or R C •+ X radical cations does not involve direct photoionization of orbitals of the substituents X.Photoelectron spectroscopy is used to determine the energy E (ionization potentials I) of valence electrons. The radical cation R C •+ BX is formed upon detachment of an outer (valence) electron from R C under the action of photoelectrons hν with energy of about tens of electron

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Section: 22mentioning

confidence: 99%

“…The reaction series of compounds R C BX participating in ionization processes (1) can be divided into so called classical and non classical ones (see, for example, 22).…”

Section: 22mentioning

confidence: 99%