A study of the electronic structure and properties of the propargyl radical

Abstract

By means of B3LYP/6-311++G(3df,3pd) the electron density distribution in the propargyl radical CH₂CCH is obtained. Within the Quantum Theory of Atoms in Molecules the phenomenon of conjugation and the spin density distribution of the unpaired electron in CH₂CCH are studied at the qualitative level. Characteristics of the electronic structure of CH₂CCH and its parent molecules CH₃–C≡CH and CH₂=C=CH₂ are compared. With the use of the rigid rotator-anharmonic oscillator model the thermodynamic properties of the propargyl radical and enthalpies of bond cleavage in propyne and allene are calculated in the temperature range 298-1500 K. The relationship between the electronic and thermodynamic properties of CH₂CCH is considered and its conjugation energy is calculated.