Pulsed laser fields pump photonics

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

From a frequency domain point of view, a femtosecond pump-probe experiment, shown schematically in Fig. 1, is a sum of coherent two-photon transition amplitudes constrained by the pump and probe laser bandwidths. The measured signal is proportional to the population in the final state Tf) at the end of the two-pulse sequence. As these two-photon transitions are coherent, we must therefore add the transition amplitudes and then square in order to obtain the probability. As discussed below, the signal contains interferences between all degenerate two-photon transitions. When the time delay between the two laser fields is varied, the... 

Besides various detection mechanisms (e.g. stimulated emission or ionization), there exist moreover numerous possible detection schemes. For example, we may either directly detect the emitted polarization (oc PP, so-called homodyne detection), thus measuring the decay of the electronic coherence via the photon-echo effect, or we may employ a heterodyne detection scheme (oc EP ), thus monitoring the time evolution of the electronic populations In the ground and excited electronic states via resonance Raman and stimulated emission processes. Furthermore, one may use polarization-sensitive detection techniques (transient birefringence and dichroism spectroscopy ), employ frequency-integrated (see, e.g. Ref. 53) or dispersed (see, e.g. Ref. 54) detection of the emission, and use laser fields with definite phase relation. On top of that, there are modern coherent multi-pulse techniques, which combine several of the above mentioned options. For example, phase-locked heterodyne-detected four-pulse photon-echo experiments make it possible to monitor all three time evolutions inherent to the third-order polarization, namely, the electronic coherence decay induced by the pump field, the djmamics of the system occurring after the preparation by the pump, and the electronic coherence decay induced by the probe field. For a theoretical survey of the various spectroscopic detection schemes, see Ref. 10. 

The main cost of this enlianced time resolution compared to fluorescence upconversion, however, is the aforementioned problem of time ordering of the photons that arrive from the pump and probe pulses. Wlien the probe pulse either precedes or trails the arrival of the pump pulse by a time interval that is significantly longer than the pulse duration, the action of the probe and pump pulses on the populations resident in the various resonant states is nnambiguous. When the pump and probe pulses temporally overlap in tlie sample, however, all possible time orderings of field-molecule interactions contribute to the response and complicate the interpretation. Double-sided Feymuan diagrams, which provide a pictorial view of the density matrix s time evolution under the action of the laser pulses, can be used to detenuine the various contributions to the sample response [125]. 

Figure 1 Schematic representation of a time-resolved coherent Raman experiment, (a) The excitation of the vibrational level is accomplished by a two-photon process the laser (L) and Stokes (S) photons are represented by vertical arrows. The wave vectors of the two pump fields determine the wave vector of the coherent excitation, kv. (b) At a later time the coherent probing process involving again two photons takes place the probe pulse and the anti-Stokes scattering are denoted by subscripts P and A, respectively. The scattering signal emitted under phase-matching conditions is a measure of the coherent excitation at the probing time, (c) Four-photon interaction scheme for the generation of coherent anti-Stokes Raman scattering of the vibrational transition.

The adiabatic passage induced by two delayed laser pulses, the well-known process of STIRAP [69], produces a population transfer in A systems (see Fig. 7a). The pump field couples the transition 1-2, and the Stokes field couples the transition 2-3. It is known that, with the initial population in state 11), a complete population transfer is achieved with delayed pulses, either (i) with a so-called counterintuitive temporal sequence (Stokes pulse before pump) for various detunings as identified in Refs. 73 and 74 or (ii) with two-photon resonant (or quasi-resonant) pulses but far from the one-photon resonance with the intermediate state 2), for any pulse sequence (demonstrated in the approximation of adiabatic elimination of the intermediate state [75]). Here we analyze the STIRAP process through the topology of the associated surfaces of eigenenergies as functions of the two field amplitudes. Our results are also valid for ladder and V systems. 

The sketch of the experimental set-up is shown in Figure 1. A Q-switched Nd-YAG laser, operating at 1.06 ixm and a pulse repetition 2-12.5 Hz was used to provide the fundamental (pump) beam. The peak power was 200-300 kW. The beam was focused with a 43 cm lens so that the power density on the sample placed in a thermostate was about 100-200 MW-cm. " For investigation the field-induced SHG, short pulses (tp = 20 fxs) of high voltage Up = 4kV) were provided by an electrical generator. The pulse duration was chosen from the condition Trelaxation time for dipolar (Debye) polarization, and T is the director reorientation time. Under such a condition, molecular dipoles are oriented by the field but the Fredericks transition does not take place. The sensitivity of our set-up was about 30 photons of the optical second harmonic per single laser pulse. The cell temperature was stabilized with an accuracy of 0.1° K. 

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