화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.109, No.23, 5176-5185, 2005
A numerical simulation of nonadiabatic electron excitation in the strong field regime: Linear polyenes
Time-dependent Hartree-Fock theory has been used to study of the electronic optical response of a series of linear polyenes in strong laser fields. Ethylene, butadiene, and hexatriene have been calculated with 6-31G(d,p) in the presence of a field corresponding to 8.75 x 10(13) W/cm(2) and 760 nm. Time evolution of the electron population indicates not only the pi electrons, but also lower lying valence electrons are involved in electronic response. When the field is aligned with the long axis of the molecule, Lowdin population analysis shows large charges at each end of the molecule. For ethylene, the instantaneous dipole moment followed the field adiabatically, but for hexatriene, nonadiabatic effects were very pronounced. For constant intensity, the nonadiabatic effects in the charge distribution, instantaneous dipole, and orbital populations increased nonlinearly with the length of the polyene. These calculations elucidate the mechanism of the strong field nonadiabatic electron excitation of polyatomic molecules leading to their eventual ionization and fragmentation. The described computational methods are a viable tool for studying the complex processes in multielectron atomic and molecular systems in strong laser fields.