Improvement of the Parametric Method of the Theory of Vibronic Spectra of Polyatomic Molecules: Absorption Spectra and the Structure of Butadiene, Hexatriene, and Octatetraene in the Excited State

摘要

The structure of the excited states and absorption spectra of butadiene, hexatriene, and octatetraene are calculated by the parametric method of the theory of vibronic spectra using models of the first- and secondorder approximations. It is shown that these molecular models adequately reflect the molecular structure and allow one to predict quantitatively the shape and fine vibrational structure of the absorption spectra. When passing to the second-order approximation, only two additional (angular) parameters are used. These parameters are transferable in the series of polyenes. Compared to the first-order approximation model, the second-order approximation model more accurately takes into account the angular deformations of polyenes upon their excitation and describes the intensity distribution in the vibrational spectrum, including weak lines. In addition, the calculations also quantitatively predict spectral variations in the molecular series. The parametric method is more efficient for modeling polyatomic molecules in the excited states and their vibrational spectra compared to other semiempirical and ab initio methods.