The (A)over-tilde(2)E(B)over-tilde(2)B(2) photoelectron bands of allene beyond the linear coupling scheme: an ah initio dynamical study including all fifteen vibrational modes

In an earlier publication [J. Chem. Phys. 1999, 111, 10452] we theoretically investigated the photoelectron spectrum of allene (C3H4+) pertinent to the Ã2E/B̃2B2 interacting electronic manifold of its radical cation (C3H4+). Employing a linear vibronic coupling scheme it was demonstrated that in addition to the E⊗B Jahn−Teller activity within the 2e electronic manifold, there is a strong (E⊗B) + E pseudo-Jahn−Teller interaction with the B̃2B2 electronic state, which causes the diffuse structures observed at high energies. Here, the same photoelectron spectrum is reinvestigated including all fifteen vibrational degrees of freedom of the system and a higher order coupling scheme. The coupling parameters of the Hamiltonian are calculated by ab initio methods. The photoelectron band is calculated by the wave packet propagation method within the multiconfiguration time-dependent Hartree (MCTDH) scheme and compared with the experimental results of Baltzer et al. [Chem. Phys. 1995, 196, 551]. The progressions at low energies are identified unambiguously by calculating the "stick" vibronic spectrum within the Ã2E electronic manifold, considering five relevant vibrational modes, and the effect of the higher order couplings is clearly demonstrated. The calculations show that it is necessary to re-assign the progressions in the low-energy region of the spectrum to the vibrational mode v3, which is of C=C stretching and H—C—H bending character and the combination of symmetric (v2) and antisymmetric (v7) H—C—H bending vibrational modes. In addition, we report on the time-dependent nuclear dynamics by snapshots of the time-evolved wave packet and by the diabatic electronic populations

Simulation of a complex spectrum: Interplay of five electronic states and 21 vibrational degrees of freedom in C5H4+

Using a five-state, all-mode vibronic coupling model Hamiltonian derived in a previous publication [A. Markmann et al., J. Chem. Phys.122, 144320 (2005)], we have calculated the photoelectron spectrum of the pentatetraene cation in the neighborhood of the B`2E state, which can be represented with charge-localized components. To this end, quantum nuclear dynamics calculations were performed using the multiconfiguration time-dependent Hartree method, taking all 21 vibrational normal modes into account. Compared to experiment, the main features are reproduced but higher accuracy experiments are necessary to gauge the accuracy of the predictions for the vibronic progressions at the rising flank of the spectrum