Cascaded free-induction decay four-wave mixing

We report the observation of cascaded optical free-induction decay four-wave mixing (FID-FWM) signal. This process can take place when nonlinear optical measurements are carried out with pulses that are orders of magnitude shorter than the dephasing time of the sample. Experimental observations and theoretical calculations show that the coherent emission from the first laser pulse participates as a time-delayed local electric field to yield the cascaded signal. We arrive at this conclusion based on pulse sequences of degenerate noncollinear femtosecond pulses for which three-pulse FWM is forbidden. Further confirmation was obtained from experiments where the time delay between two pulses were used to form ground or excited state populations, the signal reflected the corresponding ground or excited state dynamics. Although FID is long lived, the femtosecond resolution was found to be maintained in our measurements on gas phase molecular iodine. This is because the FID is modulated in the femtosecond time scale by the molecular dynamics of the system; its intensity and modulation were confirmed using femtosecond time-gated upconversion measurements. (C) 2001 Elsevier Science B.V. All rights reserved.Symposium on Multidimensional Spectroscopies held at the APS Meeting, Mar, 2000, Minneapolis, M

Femtosecond spectrally dispersed three-pulse four-wave mixing: the role of sequence and chirp in controlling intramolecular dynamics

The roles of pulse sequence and pulse chirp were explored using femtosecond three-pulse four-wave mixing (FWM), The experiments were carried out on gas-phase It and the degenerate laser pulses are resonant with the transition between the X ((1)Sigma g+) ground and B ((3)Pi(0u+)) excited electronic states. Impulsive excitation leads to the observation of vibrational coherence in the ground and the excited states. Control over the observed population and vibrational coherence is achieved by using specific pulse sequences. Using chirped pulses results in changes in vibrational coherence. When the PWM signal is spectrally dispersed, the two-dimensional data (wavelength and time delay) provide important spectroscopic information about the intramolecular dynamics of both electronic states. This information is not typically available in time or spectrally integrated measurements. A theoretical foundation for these observations based on the density matrix formalism is briefly discussed. Copyright (C) 2000 John Wiley and Sons, Ltd

Sequences for controlling laser excitation with femtosecond three-pulse four-wave mixing

Three-pulse four-wave mixing (FWM) is used here to study and control laser excitation processes. For general laser excitation processes, after a molecule interacts resonantly with a laser pulse, the molecule has a probability of being in the ground or in the excited state. Control over this process depends on the phase and amplitude of the electric fields that interact with the molecular system. Here we show how three-pulse FWM can be used to control the excitation of iodine molecules. Depending on the time delay between the first two pulses, the observed signal reflects the dynamics of the ground or excited state. A theoretical formalism based on the density matrix formulation is presented and solved for a four-level system. Experiments are found to be in excellent agreement with the theory. The influence of linear chirp on three-pulse FWM experiments is explored. Spectrally dispersed three-pulse FWM is found to be extremely useful for studying the effect of chirp on laser excitation of molecular systems. Experimental demonstrations of these effects are included

Control and characterization of intramolecular dynamics with chirped femtosecond three-pulse four-wave mixing

Experimental control and characterization of intramolecular dynamics are demonstrated with chirped femtosecond three-pulse four-wave mixing (FWM). The two-dimensional (spectrally dispersed and time-resolved) three-pulse FWM signal is shown to contain important information about the population and coherence of the electronic and vibrational states of the system. The experiments are carried out on gas-phase I-2 and the degenerate laser pulses are resonant with the X (ground) to B (excited) electronic transition. In the absence of laser chirp, control over population and coherence transfer is demonstrated by selecting specific pulse sequences. When chirped lasers are used to manipulate the optical phases of the pulses, the two-dimensional data demonstrate the transfer of coherence between the ground and excited states. Positive chirps are also shown to enhance the signal intensity, particularly for bluer wavelengths. A theoretical model based on the multilevel density matrix formalism in the perturbation limit is developed to simulate the data. The model takes into account two vibrational levels in the ground and the excited states, as well as different pulse sequences and laser chirp values. The analytical solution allows us to predict particular pulse sequences that control the final electronic state of the population. In a similar manner, the theory allows us to find critical chirp values that control the transfer of vibrational coherence between the two electronic states. Wave packet calculations are used to illustrate the process that leads to the observation of ground-state dynamics. All the calculations are found to be in excellent agreement with the experimental data. The ability to control population and coherence transfer in molecular systems is of great importance in the quest for controlling the outcome of laser-initiated chemical reactions

Population and coherence control by three-pulse four-wave mixing

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. (C) 1999 American Institute of Physics. [S0021-9606(99)03233-X]

The role of pulse sequences in controlling ultrafast intramolecular dynamics with four-wave mixing

This article seeks to provide a fundamental understanding of time-resolved four-wave mixing (FWM) processes based on a large body of experimental measurements on a model system consisting of isolated iodine molecules. The theoretical understanding is based primarily on a diagrammatic approach. Double-sided Feynman diagrams are used to classify and describe the coherent FWM processes involved in the signal obtained with each pulse sequence. Different pulse sequences of degenerate femtosecond pulses are shown to control the optical phenomena observed, that is transient grating, reverse-transient grating, photon echo and virtual photon echo. The experimental data reveal clear differences between the nonlinear optical phenomena. We find that the virtual photon echo sequence k(1) - k(2) + k(3) is the most efficient for controlling the observation of ground-or excited-state dynamics. The strategy followed to make this assessment was to compare transients when the time delay between two of the three pulses set in or out of phase with the excited-state vibrational dynamics. We have obtained a signal from pulse sequences k(1) + k(2) - k(3) for which FWM signal generation for this two-electronic-level system is forbidden. This signal can be explained by the cascading of a first-order polarization and a second-order process to generate the FWM signal. The implications of our findings are discussed in the context of multiple-pulse methods for the control of intramolecular dynamics