Excitation, preparation

In the beginning, MQ coherences are excited (preparation period) and evolve for an evolution time tj. At the end of the evolution period, the MQ coherences are reconverted to detectable single-quantum (SQ) coherences (mixing period) which then are detected. 

The laser excitation prepares the atoms in the lowest energy Stark state with m =2 in a chosen n-manifold (n=24 for example) (see Fig. 1-b). This excitation is itself a stepwise process involving three pulsed dye laser beams in resonance with the 2S-2P, 2P-3D and 3D-n, m =2, nx=0 transitions... 

Figure 3. Level diagram and fluorescence spectrum representing the dispersed fluorescence characteristics to be expected from a set of coupled vibrational levels in St. Excitation prepares the zero-order a) state (indicated by the asterisk), which then undergoes IVR. Emission gaining its strength from a) is termed vibrationally unrelaxed and tends to occur in the blue region of the...

On the other hand, if the initial excitation prepares one of higher vibronic states in the (j) manifold, this state will be coupled to the lower (s ) levels as well, as to the / levels. The vibrational relaxation within the... 

The validity of the physics that adopts the point of view of decaying states depends on the characteristics of the process of excitation-preparation. Specifically, one must assume that the duration of the pulse of excitation energy is much shorter than the lifetime of the unstable state. This implies that indeed the system is prepared in a nonstationary state at f = 0, i.e., in the localized state (T o/ Eo)/ while losing memory of the excitation step. For long-lived unstable states, this is expected to be achievable easily. For shortlived unstable atomic or molecular states, say of the order of 10 s, this is also achievable, in principle, via modern pump-probe techniques with time-delays in the range of a few femtoseconds or of a couple of hundreds of attoseconds. 

Fig. 5. A F>art of room temperature PL of EUM0O4 microstructures (Ai - A3) excitation spectra (monitored at 643 nm) and emission spectra (under 443 nm excitation) prepared by modulating the reaction time.

An alternative perspective is as follows. A 5-frmction pulse in time has an infinitely broad frequency range. Thus, the pulse promotes transitions to all the excited-state vibrational eigenstates having good overlap (Franck-Condon factors) with the initial vibrational state. The pulse, by virtue of its coherence, in fact prepares a coherent superposition of all these excited-state vibrational eigenstates. From the earlier sections, we know that each of these eigenstates evolves with a different time-dependent phase factor, leading to coherent spatial translation of the wavepacket. 

Figure Al.6,8 shows the experimental results of Scherer et al of excitation of I2 using pairs of phase locked pulses. By the use of heterodyne detection, those authors were able to measure just the mterference contribution to the total excited-state fluorescence (i.e. the difference in excited-state population from the two units of population which would be prepared if there were no interference). The basic qualitative dependence on time delay and phase is the same as that predicted by the hannonic model significant interference is observed only at multiples of the excited-state vibrational frequency, and the relative phase of the two pulses detennines whether that interference is constructive or destructive.

Second-order effects include experiments designed to clock chemical reactions, pioneered by Zewail and coworkers [25]. The experiments are shown schematically in figure Al.6.10. An initial 100-150 fs pulse moves population from the bound ground state to the dissociative first excited state in ICN. A second pulse, time delayed from the first then moves population from the first excited state to the second excited state, which is also dissociative. By noting the frequency of light absorbed from tlie second pulse, Zewail can estimate the distance between the two excited-state surfaces and thus infer the motion of the initially prepared wavepacket on the first excited state (figure Al.6.10 ). 

Figure Al.6.24. Schematic representation of a photon echo in an isolated, multilevel molecule, (a) The initial pulse prepares a superposition of ground- and excited-state amplitude, (b) The subsequent motion on the ground and excited electronic states. The ground-state amplitude is shown as stationary (which in general it will not be for strong pulses), while the excited-state amplitude is non-stationary. (c) The second pulse exchanges ground- and excited-state amplitude, (d) Subsequent evolution of the wavepackets on the ground and excited electronic states. Wlien they overlap, an echo occurs (after [40]).

While monomolecular collision-free predissociation excludes the preparation process from explicit consideration, themial imimolecular reactions involve collisional excitation as part of the unimolecular mechanism. The simple mechanism for a themial chemical reaction may be fomially decomposed into tliree (possibly reversible) steps (with rovibronically excited (CH NC) ) ... 

To detect tlie initial apparent non-RRKM decay, one has to monitor the reaction at short times. This can be perfomied by studying the unimolecular decomposition at high pressures, where collisional stabilization competes with the rate of IVR. The first successful detection of apparent non-RRKM behaviour was accomplished by Rabinovitch and co-workers [115], who used chemical activation to prepare vibrationally excited hexafluorobicyclopropyl-d2 ... 

Modem photochemistry (IR, UV or VIS) is induced by coherent or incoherent radiative excitation processes [4, 5, 6 and 7]. The first step within a photochemical process is of course a preparation step within our conceptual framework, in which time-dependent states are generated that possibly show IVR. In an ideal scenario, energy from a laser would be deposited in a spatially localized, large amplitude vibrational motion of the reacting molecular system, which would then possibly lead to the cleavage of selected chemical bonds. This is basically the central idea behind the concepts for a mode selective chemistry , introduced in the late 1970s [127], and has continuously received much attention [10, 117. 122. 128. 129. 130. 131. 132. 133. 134... 

The time evolution of is shown in figure A3.13.12 for the field free motion of wave packets for CHD2T and CHDT2 prepared by a preceding excitation along the> -axis. 

Quack M 1982 Reaction dynamics and statistical mechanics of the preparation of highly excited states by intense infrared radiation Adv. Chem. Rhys. 50 395-473... 

Plenary 11. W Kiefer et al, e-mail address wolfgang.kiefer mail.imi-wue.de (TR CARS). Ultrafast impulsive preparation of ground state and excited state wavepackets by impulsive CARS with REMPI detection in potassium and iodine duners. 

Plenary 7 7. P M Champion et al, e-mail address champ neu.edu (TRRRS). Femtosecond impulsive preparation and timing of ground and excited state Raman coherences in heme proteins. Discovery of coherence transfer along a de-ligation coordinate. See above for fiirther connnent. 

The adliesion and fiision mechanisms between bilayers have also been studied with the SEA [M, 100]. Kuhl et al [17] found that solutions of short-chained polymers (PEG) could produce a short-range depletion attraction between lipid bilayers, which clearly depends on the polymer concentration (fignre Bl.20.1 It. This depletion attraction was found to mduce a membrane fusion widiin 10 minutes that was observed, in real-time, using PECO fringes. There has been considerable progress in the preparation of fluid membranes to mimic natural conditions in the SEA [ ], which promises even more exciting discoveries in biologically relevant areas. 

An interferometric method was first used by Porter and Topp [1, 92] to perfonn a time-resolved absorption experiment with a -switched ruby laser in the 1960s. The nonlinear crystal in the autocorrelation apparatus shown in figure B2.T2 is replaced by an absorbing sample, and then tlie transmission of the variably delayed pulse of light is measured as a fiinction of the delay This approach is known today as a pump-probe experiment the first pulse to arrive at the sample transfers (pumps) molecules to an excited energy level and the delayed pulse probes the population (and, possibly, the coherence) so prepared as a fiinction of time. 

---