Theoretical Study of Haloacetonitrile Anions: CH_2XCN^- (X=F, Cl)

Haloacetonitrile anions CH2XCN- (X=F, Cl) were studied by HF-SCF, Becke3-LYP, and MP2 methods together with the Dunning's basis set aug-cc-PVTZ. The vertical electron attachments to the neutral are endothermic. The geometrically optimized CH2FCN- is mainly a valence-bounded anion and CH2FCN-→CH2CN+F- is a nonadiabatic dissociation. This theoretical study in good agreement with the experimental results shows that the Becke3-LYP method is reasonable in describing the electronic structures of anions and dissociative attachment dynamics, while significant differences between MP2 and Becke3-LYP results are shown for the dissociation potential curves of CH2ClCN-→CH2CN+Cl-.2,70-(Ethylene)-bis-8-hydroxyquinoline was optimized with DFT/B3LYP and ab initio HF methods, so ionization potential and electron affinity could be determined. Absorption spectrum was calculated by ZINDO and TD-DFT. CIS method was used to calculate the S1 excited states of the compound and afterwards the emission spectrum was computed. When the solvent effect was taken into account, the computed results show encouraging agreement with known experimental data. The results of analyzing the relationship between the energies and absorption spectra indicate that the ability to transporting electrons is strengthened compared with 8-hydroxyquinoline and that absorption and emission spectra are red-shifted. The intramolecular reorganization energy of tris(2,70-(ethylene)-bis-8-hydroxyquinoline)-aluminum implies its electron transporting property is worse than tris(8-hydroxyquinoline)-aluminum. The predicted maximum emission wavelength is red-shifted compared with tris(8-hydroxyquinoline)-aluminum.