Comparative study of spectroscopic properties of the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues

摘要

Semiempirical and ab initio-based CI methods have been employed to study the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues with electron-donating (methyl, isopropyl) and electron-withdrawing (fluoromethyl) groups on nitrogen. Variations of the dihedral angles (Γ3, Γ4) of the ground state have given the global minima and global maxima at (180°, 180°) and (90°, 0°) conformations, respectively, with some exceptions in the case of fluoromethyl compound. Increase in the +I effect on nitrogen shifts the TICT conical intersection point away from the 90° (Γ3 dihedral angle) value, when the Γ4 value is kept fixed at 180°. Transition moment values of the allowed S0(1Ag –like) →S1 (2Bu–like) transitions are expectedly higher than the forbidden S0(1Ag –like) →S2(2Ag –like) transitions by almost 5.6 D. Radiative lifetime values of the first excited states are calculated to be around 215 ps for all the four compounds. At (180°, 180°) conformation the vertical excitation energy (VEE) between the S0 and S1 states of the 2,4-pentadieniminium cation is found to be 3.3 eV, which corresponds to the absorption wavelength value of roughly 375 nm. The VEE value increases with substituents having +I effect on nitrogen, while for the fluoromethyl compound it is calculated to be around 2.85 eV. The energy gap between the first two excited singlet states is found to have the least value in the isopropyl-substituted compound, where the S2 state contains a huge contribution from the HOMO2→LUMO2 configuration.