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Localized state short pulse

The LIF technique is extremely versatile. The determination of absolute intermediate species concentrations, however, needs either an independent calibration or knowledge of the fluorescence quantum yield, i.e., the ratio of radiative events (detectable fluorescence light) over the sum of all decay processes from the excited quantum state—including predissociation, col-lisional quenching, and energy transfer. This fraction may be quite small (some tenths of a percent, e.g., for the detection of the OH radical in a flame at ambient pressure) and will depend on the local flame composition, pressure, and temperature as well as on the excited electronic state and ro-vibronic level. Short-pulse techniques with picosecond lasers enable direct determination of the quantum yield [14] and permit study of the relevant energy transfer processes [17-20]. [Pg.5]

A major technological innovation that opens up the possibility of novel experiments is the availability of reliable solid state (e.g., TiSapphire) lasers which provide ultra short pulses over much of the spectral range which is of chemical interest. [6] This brings about the practical possibility of exciting molecules in a time interval which is short compared to a vibrational period. The result is the creation of an electronically excited molecule where the nuclei are confined to the, typically quite localized, Franck-Condon region. Such a state is non-stationary and will evolve in time. This is unlike the more familiar continuous-wave (cw) excitation, which creates a stationary but delocalized state. The time evolution of a state prepared by ultra fast excitation can be experimentally demonstrated, [5,7,16] and Fig. 12.2 shows the prin-... [Pg.210]

But the unadorned Eqs. (9.1.5) and (9.1.6) do not make sufficiently clear the physical significance of the nonstationary,initially-localized, f (O) states that are most easily created by a short, Fourier transform limited pulse of electromagnetic radiation. Short is not an absolute quality. For a sufficiently short pulse, the nature of the initial localization prepared and the specific dynamical processes sampled depend primarily on the duration of the preparation pulse and secondarily on its spectral content (Heller, et ai, 1982 Johnson, et ai, 1996). [Pg.626]

The Eq. (9.1.16) alternative form for Ivn io) is mathematically equivalent to the standard Eq. (9.1.9) form, but in many cases Eq. (9.1.16) is both more convenient to use and provides deeper insights into how local features of the e-state potential energy surface affect the dynamical processes that are encoded in the absorption spectrum (see Figs. 9.1 and 9.2). The keys to these insights are (i) that k, (0)) is the initially localized state-function that would be produced by a sufficiently short excitation pulse and (ii) that the early time evolution of ti) generates the most prominent features of the absorption spectrum, Iv<< u)). [Pg.630]

As can be taken from the figure a localized wave packet is prepared in the short pulse excitation process. Its location is close to the potential barrier which separates the two product channels H -f- OD and D -f- Oif, i.e. the packet is found in the vicinity of the transition-state re on. Nevertheless parts of the initial wave packet have already moved towards the exit channels. Since the if-atom is lighter than the D-atom it... [Pg.285]

We used short broadband pump pulses (spectral width 200 cm 1, pulse duration 130 fs FWHM) to excite impulsively the section of the NH absorption spectrum which includes the ffec-exciton peak and the first three satellite peaks [4], The transient absorbance change signal shows pronounced oscillations that persist up to about 15ps and contain two distinct frequency components whose temperature dependence and frequencies match perfectly with two phonon bands in the non-resonant electronic Raman spectrum of ACN [3] (Fig. 2a, b). Therefore the oscillations are assigned to the excitation of phonon wavepackets in the ground state. The corresponding excitation process is only possible if the phonon modes are coupled to the NH mode. Self trapping theory says that these are the phonon modes, which induce the self localization. [Pg.563]

The postsynaptic transduction of the dopamine signal, whether steady-state, pulse increase, or the pulse decrease in concentration, depends on the relative predominance of Dl-like or D2-like dopamine receptors in the postsynaptic cell. The steady-state levels appear to be sufficient to activate both subtypes of receptor, as locally applied antagonists of either receptor subtype produce physiological effects. Two broad classes of postsynaptic effects can be identified immediate, short-term effects which reverse rapidly, and longer-term effects which persist after the removal of the dopamine signal. [Pg.227]

Transient absorption measurements have recently been recorded from the organometallic species chromium hexacarbonyl in ethanol solution [94], Absorption of a 65-fs, 310-nm excitation pulse was followed by measurement of excited-state absorption of a 65-fs, 480-nm probe pulse. The data shown in Figure 14 indicate a rapid nonexponential decay at short times followed by a gradual exponential rise. The slower feature was observed previously [95] and is known to correspond to the solvent complexation of Cr(CO)5 to yield Cr(CO)j(MeOH). The initial feature, which is observed at other probe wavelengths as well, is believed to correspond to the initial ligand loss reaction. Note that this case is different from ICN in that the initially excited wavepacket is not on the side of the Sj potential but rather (as is clear from the molecular symmetry) on a local potential maximum. The wavepacket must then spread that is, dissociation along either direction is equally likely. The rapid nonexponential decay was analyzed in terms of classical kinematics along a dissociative potential. [Pg.30]

The dump pulse optimization leads to a spatial localization of the phase space density in the objective (isomer II). For this purpose, the intermediate target operator [Eq. (22)] can be propagated on the ground state, and the dump pulse is obtained from Eqs. (17) and (21). The largest eigenvalue (e.g., 0.78) can be obtained. This corresponds to 78% efficiency of localization of isomer II. The optimized dump pulse is very short ( 20 fs cf. the part of the signal after trf = 250 fs in Fig. 11). This implies that the time window around tj for... [Pg.232]

Fluorescence lifetimes have been measmed directly by time-correlated single-photon counting for pentacene in p-terphenyl [100]. This experiment requires careful selection of the laser pulse eharaeteristies sueh that the pulse duration is short enough to resolve the 23 ns decay time, yet has a bandwidth narrow enough to allow speetral selection of individual molecules. Four different molecules had the same lifetime to within experimental uncertainty, indicating that the principal contributions to the Sj state decay (radiation and internal conversion to Sq) are not strongly sensitive to the local environment in this relatively homogeneous crystalline matrix. [Pg.2494]


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See also in sourсe #XX -- [ Pg.626 ]




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Local states

Localized states

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