Sample preparation pump-probe

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. 

The pump-probe method provides the solution to this nanosecond barrier. Here, two light pulses are generated one to excite the sample (prepare the excited state) and one to probe the system at a given time after excitation (Figure 10.8). 

The laser system consisted of a home-built Ti sapphire fs laser oscillator and regenerative amplifier (RGA). The pulse duration was 50 fs at 800 nm and 1 kHz repetition rate. The output of the RGA was split into two parts. One part was used as pump pulse. The other part served as a source for the generation of probe pulses with the help of a non-collinear optical parametric amplifier (NOPA, Clark). The sample preparation was explained elsewhere [7]. Briefly, sodium (Alfa Aesar) was used as received and sodium bromide (Alfa Aesar) was dried and re-crystallized under vacuum. The preparation of the samples was carried out in a glovebox under argon atmosphere. Localized electrons were generated by heating the metal-salt mixture to 800 °C, i.e. well above the melting point of the salt. 

The NO2 dissociation rate was measured by a two-color picosecond pump-probe method in which the product NO was monitored by LIF. Of particular significance in this study is that the NO2 density of states at the dissociation limit of 25,130.6 cm is relatively well established from an extrapolation of experimentally determined densities at an energy of 18,500 cm . This density (for cold samples where the rotations do not contribute significant densities) is 0.3 states per cm , (Miyawaki et al., 1993) which leads to a minimum rate constant l/h p( ) = 1 x 10 sec . The experimentally measured rate increases from 0 to 1.6 x 10 sec at the dissociation limit. It is interesting that the subpicosecond laser pulses with their transform limited resolution of about 20 cm do not excite individual NO2 resonance states (see section 8.3, p. 284) but, instead, prepare a superposition of those states that are optically accessible within the laser bandwidth. It is thought that all resonance states in this bandwidth are... 

The spectroscopic tool to be considered here is femtosecond pump/probe spectroscopy. This experimental technique uses two ultrashort laser pulses which are time-delayed with respect to each other. They are sent into a molecular sample and a signal is recorded as a function of the delay-time between the pulses. To be more specific, we assume the molecule to be in an inital state 0o) O). Here o) denotes the wave function for the nuclear motion and 0) the wave function of the electrons (the adiabatic separation of nuclear and electronic motion is assumed throughout). The pump pulse induces a transition and the resulting wave function which describes the molecule after the interaction with the electric field may be assigned as 0i l). We treat electronic excitation so that the molecule is prepared in another electronic state 1). After the pump pulse passed the sample, the molecule evolves unperturbed until the probe pulse starts interacting. This interaction results in a second excitation to (in our case) a final electronic state 2) with the respective nuclear wave function 1 2) The scheme just described is depicted in Figure 1 and illustrates the idea of many pump/probe experiments. 

To observe the transient spatiotemporal structure of the WP interference, we have performed the fs pump-fs probe experiment [37], The sample gas was prepared by molecular jet expansion of the mixture of iodine vapor and Ar buffer gas into a vacuum chamber. A continuous gas jet is preferable when we use a high-repetition-rate laser system. The estimated vibrational temperature was 170K[37]. 

With the ever-increasing need to improve quality and productivity in the analytical pharmaceutical laboratory, automation has become a key component. Automation for vibrational spectroscopy has been fairly limited. Although most software packages for vibrational spectrometers allow for the construction of macro routines for the grouping of repetitive software tasks, there is only a small number of automation routines in which sample introduction and subsequent spectral acquisition/data interpretation are available. For the routine analysis of alkali halide pellets, a number of commercially available sample wheels are used in which the wheel contains a selected number of pellets in specific locations. The wheel is then indexed to a sample disk, the IR spectrum obtained and archived, and then the wheel indexed to the next sample. This system requires that the pellets be manually pressed and placed into the wheel before automated spectral acquisition. A similar system is also available for automated liquid analysis in which samples in individual vials are pumped onto an ATR crystal and subsequently analyzed. Between samples, a cleaning solution is passed over the ATR crystal to reduce cross-contamination. Automated diffuse reflectance has also been introduced in which a tray of DR sample cups is indexed into the IR sample beam and subsequently scanned. In each of these cases, manual preparation of the sample is necessary (23). In the field of Raman spectroscopy, automation is being developed in conjunction with fiber-optic probes and accompanying... 

The experimental results which lead to these conclusions are summarized In Table I. Elemental analyses, conducted by a commercial laboratory, are presented In the form of a ratio of the relative numbers of atoms of C, H, N, and 0 normalized to 3 carbon atoms per monomer unit. IR spectra were obtained In-house using a Perkin Elmer 298 IR spectrophotometer. Solid probe magic angle spinning NMR experiments were performed at the National Bureau of Standards. All of these analyses were performed on bulk (l.e. pyrolyzed In batches of lg) samples of 485,000 average molecular weight ultrapure PAN prepared In a tube furnace evacuated by a mechanical vacuum pump, and are reported on In detail elsewhere.(13) Table I also summarizes electrical conductivity and optical absorption experimental results obtained using thin films of PAN solution cast In dlmethylformamlde. 

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