Numerical simulation of nonadiabatic electron excitation in the strong-field regime. 3. Polyacene neutrals and cations.
The electron optical response for a series of linear polyacenes and their molecular ions (mono and dications) in strong laser fields was studied using time-dependent Hartree-Fock theory. The interactions of benzene, naphthalene, anthracene, and tetracene with pulsed fields at a frequency of 1.55 eV and intensities of 8.77 x 10(13), 3.07 x 10(13), 1.23 x 10(13), and 2.75 x 10(12) W/cm2, respectively, were calculated using the 6-31G(d,p) basis set. Nonadiabatic processes, including nonadiabatic time evolution of the dipole moment, Löwden charges, and occupation numbers, were studied. The nonadiabatic response increased with the length of the molecule and was greatest for the molecular monocations. The only exception was tetracene, in which the very strong response of the dication was due to a near resonance with the applied field. The intensity and frequency dependence of the dipole moment response for the monocations of naphthalene and anthracene was also calculated. As the intensity increased, the population of higher-energy excited-states increased, and as the frequency increased, the excitation volume increased in good agreement with the Dykhne approximation.
Smith
Stanley M
SM
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
Li
Xiaosong
X
Markevitch
Alexei
A
Romanov
Dmitri
D
Levis
Robert J
RJ
Schlegel
H Bernhard
HB