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 (2)E 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.
Markmann
Andreas
A
Theoretische Chemie, Technische Universität München, Lichtenbergstrasse 4, 85 747 Garching, Germany. andreas.markmann@ch.tum.de
Worth
Graham A
GA
Mahapatra
Susanta
S
Meyer
Hans-Dieter
HD
Köppel
Horst
H
Cederbaum
Lorenz S
LS