Journal of Physical Chemistry A, Vol.111, No.15, 2946-2950, 2007
S-1 and S-2 excited states of gas-phase Schiff-base retinal chromophores: A time-dependent density functional theoretical investigation
In concert with the recent photoabsorption experiments of gas-phase Schiff-base retinal chromophores (Nielsen et al. Phys. Rev. Lett. 2006, 96, 018304), quantum chemical calculations using time-dependent density functional theory coupled with different functionals and under the Tamm-Dancoff approximation were made on the first two excited states (S-1 and S-2) of two retinal chromophores: 11-cis and all-trans protonated Schiff bases. The calculated vertical excitation energies (T-v) and oscillator strengths (f) are consistent with the experimental absorption bands. The experimentally observed phenomenon that the transition dipole moment (mu) of S-2 is much smaller that of S-1 was interpreted by 3D representation of transition densities. The different optical behaviors (linear and nonlinear optical responds) of the excited states were investigated by considering different strengths of external electric fields.