Zur Theorie photoinduzierter Dynamik offener Molekularsysteme: Kontrolle von Dissipation durch ultrakurze Laser-Pulse
abstract in PostScript This thesis investigates the influence of intense and ultrashort laser pulses on the photoinduced dynamics of open molecular systems. The excitation of a molecule by an optical ultrashort laser pulse induces transitions between different electronic states. This excitation process is accompanied by the dissipative processes of energy and vibrational relaxation. This excitation process is described within the method of the density matrix theory. Thereby, the derivation of the quantum master equation in the framework of the projection operator formalism demonstrates that the external fields are present in the reversible part of the equation of motion and also exert an indirect influence by acting on the dissipation superoperator which accounts for dissipation. In this thesis the field--dependency of the dissipation superoperator which is induced by the external fields is considered for the first time. By a representation of the quantum master equation in the Floquet picture, an interpretation of this field--dependent effect can be given: the frequency--dependent spectral density of the environmental modes which describe dissipation is determined at different field--dependent frequencies. Analytical investigations for the two level system demonstrate that the field dependence becomes relevant if the pulse length is comparable with the time scale on which the autocorrelation function of the environmental degrees of freedom decays.To investigate the influence on experimental quantities, a two--color pump--probe experiment for the laser dye molecule IR 125 is considered for which the spectrally and temporally resolved transmission on a femtosecond and picosecond time scale has been measured. Within the model of one effective vibrational mode the experimental data is fitted. The standard Redfield theory is used to provide a reference model. A high degree of concurrence between the theory and the results of the experiment is achieved. The exact treatment of internal conversion between the excited electronic states leads to a rise in transmission within one picosecond. It is necessary to solve the density matrix equations exactly because a comparative investigation with the nonlinear susceptibility of third order leads to a clear viation from the exact result. Starting from the reference case of field--independent dissipation, the field--dependency of the relaxation rates is determined and the influence on observables for example the relative transmission is investigated. The analytical results show that the field--dependent effect is strongest if the pulse length becomes smaller than the correlation time of the environmental modes and if the acting fields are sufficiently strong. Thereby, a control of dissipation becomes possible. An influence of the field--dependent effect on experimental observables is predicted.
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School:Humboldt-Universität zu Berlin
Source Type:Master's Thesis
Keywords:Dichtematrixtheorie Dissipation Ultrakurze Laserpulse Open Molecular Systems Control Ultrashort laser pulses Density matrix theory Photoinduced dynamics
Date of Publication:06/26/1998