A b i n i t i o study of the t r a n s-butadiene π-valence states using the effective valence shell Hamiltonian method

Abstract

Low-lying π-electron vertical excitation energies of trans-butadiene are calculated using the effective valence shell Hamiltonian method. The results are compared with previous experimental and theoretical analyses of this molecule’s congested electronic spectra. The computations employ a large basis set (126 functions) which includes both diffuse functions on the carbon atoms and polarization functions on all atoms. Good agreement is obtained with the experimentally well known vertical excitation energies to the 1 3Bu, 1 3Ag, and 1 1Bu states where deviations from experiment are only 0.01, 0.01, and 0.22 eV, respectively. We confirm the experimental assignment of a valence like 1Ag state around 7.4 eV (calculated at 7.49 eV). Likewise, a member of a symmetry allowed 3p Rydberg series (of Au or Bu symmetry) in the electron impact spectrum with origin at 7.07 eV is assigned as the 2 1Bu state (with calculated vertical excitation energy of 7.00 eV). Most experiments place the 2 1Ag state above the 1 1Bu state; however, a resonance Raman assignment places it below. Our calculated excitation to the 2 1Ag state is 0.05 eV above the 2 1Bu state, about 0.5 eV lower than previous ab initio determinations. The computed vertical excitation energies are in good agreement with the interpretation of experimental electronic spectra, are in much better agreement with experiment than previously published ab initio calculations, provide the first definitive assignment of the 2 1Bu state at 7.08 eV, and conclusively assign the 3 1Ag state at 7.4 eV. The accuracy of the large basis effective valence shell Hamiltonian is, in part, due to retention of both valence and Rydberg orbitals in the valence space, a feature which has a bearing on intruder state problems and on current semiempirical π-electron theories.