Strong vibronic coupling effects in ionization spectra: The “mystery band” of butatriene

A theory of vibronic coupling in molecules is presented and applied to butatriene. The energies and coupling constants which enter the calculation are computed using ab initio Hartree—Fock and many-body methods. The influence of the energy splitting and the coupling constants on the calculated spectrum is discussed. It is definitely shown that the “mystery band” in the photoelectron spectrum of butatriene arises from the vibronic coupling between the electronic states ²B_3g and ²B_3u. To reproduce the experimental observations it is essential to include in the calculation both totally and non-totally symmetric vibrational modes.