Two time-resolved

Knowledge of the dynamics of excited states is of major importance in understanding photophysical, photochemical and photobiological processes. Two time-resolved techniques, pulse fluorometry and phase-modulation fluorometry, are commonly used to recover the lifetimes, or more generally the parameters characterizing the S-pulse response of a fluorescent sample (i.e. the response to an infinitely short pulse of light expressed as the Dirac function S). 

There should exist a correlation between the two time-resolved functions the decay of the fluorescence intensity and the decay of the emission anisotropy. If the fluorophore undergoes intramolecular rotation with some potential energy and the quenching of its emission has an angular dependence, then the intensity decay function is predicted to be strongly dependent on the rotational diffusion coefficient of the fluorophore.(112) It is expected to be single-exponential only in the case when the internal rotation is fast as compared with an averaged decay rate. As the internal rotation becomes slower, the intensity decay function should exhibit nonexponential behavior. 

Among other examples, time-resolved luminescence has recently been applied to the detection of different trace elements (i.e., elements in very low concentrations) in minerals. Figure 1.13 shows two time-resolved emission spectra of anhydrite (CaS04). The emission spectrum just after the excitation pulse (delay 0 ms) shows an emission band peaking at 385 nm, characteristic of Eu + ions. When the emission spectmm is taken 4 ms after the pulse, the Eu + luminescence has completely disappeared, as this luminescence has a lifetime of about 10/rs. This allows us to observe the weak emission signals of the Eu + and Sm + ions present in this mineral, which in short time intervals are masked by the En + Inminescence. The trivalent ions have larger lifetimes and their luminescence still remains in the ms delay range. 

The two time-resolved spectroscopic methods CIDNP [26,27] and ESR [28-30] as well as classical triplet quenching experiments all indicate that a-GAV decomposes through both triplet and singlet states in protic solvents and exclusively through the singlet state in aprotic solvents. 

We summarize here two time-resolved spectroscopic methods, giving direct information on picosecond and nanosecond photodynamics of solid surface. One is a fluorescence spectroscopy which analyzes fluorescence behavior of the surface area excited by the evanescent laser pulse. The other is to get transient UV-visible absorption spectra by using the evanescent light as a probe beam. 

Two time-resolved CIDNP investigations of hydrogen transfer were reported, in which the rates of hydrogen exchange between carbonyl compounds (benzaldehyde and benzophenone [97a] benzoquinone [97b]) and their ketyl radicals were measured. The experiments also yielded the homogeneous recombination rate of the radicals. 

The relaxation behavior at pH 1 is very interesting, but we could not analyze it because the time-resolved emission bands were bimodal. We studied the possibility of analyzing complex time-resolved spectra and in our recent paper [135] we describe a successful method of decomposition and treatment of bimodal time-resolved spectra. We used two probes with the same fluorescent headgroup differing in the length of the aliphatic tail. They have different affinity to micelles that allows study of their partitioning between micelles and bulk solvent. A detailed description and extended discussion exceeds, unfortunately, the scope of this paper, but we not only succeeded in treating the two time-resolved contributions (from free and micelle-solubilized probes) separately, but we also identified a slow contribution due to the... 

Two time-resolved fluorescence techniques, pulse Jluorimetry and phase-modulation fluorimetjy, are commonly employed to recover the lifetimes. The former uses a short exciting pulse (from femtoseconds to nanoseconds) of light, which leads to the pulsed response of the sample, which should then be deconvolved from the instrument response. In phase-modulation fluorimetry, the intensity of light used for excitation is modulated at a frequency whose reciprocal is similar to the fluorescence decay time. The sample response is also modulated, but with a time delay, measured as phase shift, from which the emission decay time can be calculated. Thus, the first technique works in the time domain, while the second one in the frequency domain. The most widely used technique in the time domain is the time-correlated single-photon counting [10, 11]. The merits of both techniques have been extensively discussed [12]. 

Petek H and Ogawa S 1997 Femtosecond time-resolved two-photon photoemission studies of electron dynamics in metals Prog. Surf. Sc/. 56 239... 

Time-resolved spectroscopy has become an important field from x-rays to the far-IR. Both IR and Raman spectroscopies have been adapted to time-resolved studies. There have been a large number of studies using time-resolved Raman [39], time-resolved resonance Raman [7] and higher order two-dimensional Raman spectroscopy (which can provide coupling infonuation analogous to two-dimensional NMR studies) [40]. Time-resolved IR has probed neutrals and ions in solution [41, 42], gas phase kmetics [42] and vibrational dynamics of molecules chemisorbed and physisorbed to surfaces [44]- Since vibrational frequencies are very sensitive to the chemical enviromnent, pump-probe studies with IR probe pulses allow stmctiiral changes to... 

With the advent of short pulsed lasers, investigators were able to perfonn time resolved coherent Raman scattering. In contrast to using femtosecond pulses whose spectral widtii provides the two colours needed to produce Raman coherences, discussed above, here we consider pulses having two distinct centre frequencies whose difference drives the coherence. Since the 1970s, picosecond lasers have been employed for this purpose [113. 114], and since the late 1980s femtosecond pulses have also been used [115]. Flere we shall briefly focus on the two-colour femtosecond pulsed experiments since they and the picosecond experiments are very similar in concept. 

In a typical time-resolved SHG (SFG) experiment using femtosecond to picosecond laser systems, two (tlnee) input laser beams are necessary. The pulse from one of the lasers, usually called the pump laser, induces the... 

Recently, a unique approach for using the correlation fiinction method has been demonstrated to extract morphological variables in crystalline polymers from time-resolved syncluotron SAXS data. The principle of the calculation is based on two alternative expressions of Porod s law using the fonu of interference fiinction [33. 36]. This approach enables a continuous estimate of the Porod constant, corrections for liquid scattering... 

Jent F, Paul H and Fischer H 1988 Two-photon processes in ketone photochemistry observed by time-resolved ESR spectroscopy Chem. Phys. Lett. 146 315-19... 

Figure Bl.23.11. Above selected time-resolved SARIS images of 4 keV Ar scadering from Pt l 11 ] along (I 12). Below view of Pt 111 ] surface along (112) showing Ar scadering from a first-lay er Pt atom (1) and spliding into two focused beams by an atomic lens fonned by neighbouring first-layer Pt atoms (2, 3, 4).

Figure B2.1.9 Two-dimensional time-resolved IR holebiiming speetra obtained with two small polypeptides, apamin and seyllatoxin, by Hoehstrasser and eo-workers [M]- Figure eourtesy Professor R M Hoehstrasser (University of Peimsylvania).

Brand L, Eggeling C, Zander C, Drexhage K FI and Seidel CAM 1997 Single-molecule identification of coumarin-120 by time-resolved fluorescence detection comparison of one- and two-photon excitation in solution J. Chem. Phys. A 101 4313-21... 

Prompt instrumentation is usually intended to measure quantities while uniaxial strain conditions still prevail, i.e., before the arrival of any lateral edge effects. The quantities of interest are nearly always the shock velocity or stress wave velocity, the material (particle) velocity behind the shock or throughout the wave, and the pressure behind the shock or throughout the wave. Knowledge of any two of these quantities allows one to calculate the pressure-volume-energy path followed by the specimen material during the experimental event, i.e., it provides basic information about the material s equation of state (EOS). Time-resolved temperature measurements can further define the equation-of-state characteristics. 

The objective in these gauges is to measure the time-resolved material (particle) velocity in a specimen subjected to shock loading. In many cases, especially at lower impact pressures, the impact shock is unstable and breaks up into two or more shocks, or partially or wholly degrades into a longer risetime stress wave as opposed to a single shock wave. Time-resolved particle velocity gauges are one means by which the actual profile of the propagating wave front can be accurately measured. 

Another error can arise when two partially resolved peaks are asymmetrical, e.g., the rear half of the peak is broader the front half. In such a situation, it is clear that there can be two sources of error, which are depicted in Figure 4. Firstly, the retention times, as measured from the peak envelope, will not be accurate. Secondly, because the peaks are asymmetrical (and most LC peaks tend to be asymmetrical to the extent shown in the Figure 4), the second peak appears higher. This can incorrectly imply that the second solute is present at a higher concentration in the mixture than the first. It follows that it is important to know the value of the specific separation ratio above which accurate measurements can still be made on the peak maxima of the individual peaks. The apparent peak separation ratio, relative to the actual peak separation ratio for columns of different efficiency, are shown in Figure 5. The data has been obtained from theoretical equations. 

Several laser systems have been used in our time-resolved PM measurements. For the ultrafast measurements, a colliding pulse mode-locked (CPM) dye laser was employed [11]. Its characteristic pulsewidth is about 70 fs, however, its wavelength is fixed at 625 nin (or 2.0 cV). For ps measurements at various wavelengths two synchronously pumped dye lasers were used (12], Although their time resolution was not belter than 5 ps, they allowed us to probe in the probe photon energy range from 1.25 cV to 2.2 cV. In addition, a color center laser... 

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