Abstract
The first vertical ionization potentialsl1 of molecules RπX (X=Ph, H2C=CH, and HC≡C) depend on the joint influence of the inductive, resonance, and polarizability effects of substituents X, which are characterized by parameters σ1, σR+, and σα, respectively. The mechanism of conjugation in radical cations formed upon ionization of RπX is changed as compared to neutral RπX molecules, while the substituent X becomes polarized. The conjugation and polarizability effects are strenthened in the sequence Ph < H2C=CH <HC≡C as Rπ changes from Ph to H2C=CH and HC≡C. The σR+ parameters of Si-, Ge-, and Sn-containing substituents X are dependent on the type of Rπ but are connected by linear dependences in the series of benzene, ethylene, and acetylene derivatives.
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