Mechanisms and optimal experimental conditions in coherent control still intensely stimulate debates. In this work, a phase-only control mechanism in an open quantum system is investigated experimentally and numerically. Several parameterizations for femtosecond pulse shaping (combination of chirp and multipulses) are exploited in transient absorption of a prototype organic molecule to control population and vibrational coherence in ground and excited states. Experimental results are further numerically simulated and corroborated with a four-level density-matrix model, which reveals a phase-only control mechanism based on the interaction between the tailored phase of the excitation pulse and the induced transient absorption. In spite of performing experiment and numerical simulations in the linear regime of excitation, the control effect amplitude depends non-linearly on the excitation energy and is explained as a pump-dump control mechanism. No evidence of single-photon control is observed with the model. Moreover, our results also show that the control effect on the population and vibrational coherence is highly dependent on the spectral detuning of the excitation spectrum. Contrary to the popular belief in coherent control experiments, spectrally resonant tailored excitation will lead to the control of the excited state only for very specific conditions.
Control of coherence and population transfer between the ground and excited states is reported using three-pulse four-wave mixing. The inherent vibrational dynamics of the system are utilized in timing the pulse sequence that controls the excitation process. A slight alteration in the pulse sequence timing causes a change in the observed signal from coherent vibration in the ground state to coherent vibration in the excited state. This control is demonstrated experimentally for molecular iodine. The theoretical basis for these experiments is discussed in terms of the density matrix for a multilevel system.
We investigate the effect of chirped excitation and the excitation detuning on the coherent control of population transfer and vibrational states in a four-level system. Density matrix equations are studied for optimally enhanced processes by considering specific parameters typical of oxazine systems. Our simulations show a strong dependence on the interplay between chirp and excitation detuning and predict enhancement factors up to 3.2 for population transfer and up to 38.5 for vibrational coherences of electronic excited states. The study of the dynamics of the populations and vibrational coherences involved in the four-level system allows an interpretation of the different enhancement/suppression processes observed.
The dynamics of populations of the vibrational states in a NO molecule (one-photon absorption) and of the electronic states in a 4,4'-bis(dimethylamino) stilbene molecule (two-photon absorption) is studied versus the frequency, intensity and shape of the laser pulse. We show that specially designed infrared laser pulses can build selective populations of certain vibrational states. A detuning of light frequency from the vibrational resonance qualitatively changes the dynamics of populations. It is found out that the populations of the nonresonant levels follow the pulse shape adiabatically if the detuning significantly exceeds the inverse characteristic time of the change of the pulse. Depopulation of the nonresonant vibrational states leads to a high population of the resonant state at the end of the pulse. Complete breakdown of the standard rotating wave approximation for a two-photon absorption process is observed even for a rather small intensity of the laser pulse. An analytical solution for the interaction of a pulse with a three-level system beyond the rotating wave approximation is obtained, and it is in close agreement with the strict numerical solution of the amplitude equations. Special attention is paid to the population dynamics of randomly oriented molecules. The orientational disorder as well as the vibrations limit the coherent population transfer. Calculations show the strong role of the anisotropy of photoexcitation in the coherent control of populations which can affect the anisotropy of photobleaching.
We have theoretically investigated the vibrational population transfer in the presence of manifolds of rotational levels in a model 15-level
Li2 molecular system by stimulated Raman adiabatic passage with intense unchirped femtosecond laser pulses. We have considered five rotational levels
Jg=0,2,…,8 associated with the initial vibrational level
vg=0 of the ground electronic state $X\text{ }{^{1}\ensuremath{\Sigma}}_{g}^{+}$, five rotational levels
Ji=1,3,…,9 associated with the vibrational level
vi=1 of the intermediate excited electronic state $A\text{ }{^{1}\ensuremath{\Sigma}}_{u}^{+}$, and five rotational levels
Jf=0,2,…,8 associated with the final target vibrational levels
vf=1,2 of the $X\text{ }{^{1}\ensuremath{\Sigma}}_{g}^{+}$ state of the
Li2 alkali dimer. The pump and Stokes laser pulses are taken to have the same temporal (Gaussian) shapes, pulse widths, and linear parallel polarizations. The laser wavelengths are in the (visible) range of 700--740 nm. The (peak) intensities of the pulses are of the order of $1\ifmmode\times\else\texttimes\fi{}{10}^{12}--2.5\ifmmode\times\else\texttimes\fi{}{10}^{13}\text{ }\text{W}/{\text{cm}}^{2}$ and the pulse widths are of the order of 20--50 fs. We have solved the 15 coupled time-dependent Schr\"odinger equations to study the population transfer to the target-excited vibrational levels. We have observed that, even with ``mushrooming'' of closely spaced rotational levels, efficient and selective population transfer to excited vibrational levels in
Li2 alkali dimer can be achieved for counterintuitive pulse sequence by controlling the pump and Stokes laser parameters. We have endeavored to explain the results within the framework of adiabatic picture.