Pump-probe spectroscopy instrumentation

Ellington et al.40) used femtosecond pump-probe spectroscopy to probe directly the arrival of electrons injected into the TiOz film with near- and mid-IR that probe the absorption at 1.52 jum and in the range of 4.1-7.0 jUm. Their measurements indicate an instrument limited 50 fsec upper limit on the electron injection time. These observations suggest that electron injection from Dye 2 to... 

Abstract. We present a novel instrument combining femtosecond pump-probe spectroscopy with broadband detection and confocal microscopy. The system has 200-fs temporal resolution and 300-nm spatial resolution. We apply the instrument to map excited state dynamics in thin films of polyfluorene-polymethylethacrylate blends. 

Fig. 6.8 Femtosecond pump-probe spectroscopy of diiodoBODIPY (10). (a) Inverted absorption spectrum (6) and transient absorption spectra at 0.5 (1), 20 (2), 50 (3), 110 (4), and 350 (5) ps delay between pump and probe pulses, (b) Differential absorption spectra of intermediate states obtained after modeling the experimental data by a three-exponential equation (see text) that is convoluted with the instrumental response function (1) zero delay (sum of all amplitudes, S2 state), (2) ultrafast relaxation of the S2 state (sum of A2, A3, A4 amplitudes), (3) thermalized Sj state (sum of A3 and A4 amplitudes), (4) Tj state (A4 amplitude). Reprinted with permission from [24]...

The high costs associated with specialist ultrafast laser techniques can make their purchase prohibitive to many university research laboratories. However, centralised national and international research infrastructures hosting a variety of large scale sophisticated laser facilities are available to researchers. In Europe access to these facilities is currently obtained either via successful application to Laser Lab Europe (a European Union Research Initiative) [35] or directly to the research facility. Calls for proposals are launched at least annually and instrument time is allocated to the research on the basis of peer-reviewed evaluation of the proposal. Each facility hosts a variety of exotic techniques, enabling photoactive systems to be probed across a variety of timescales in different dimensions. For example, the STFC Central Laser Facility at the Rutherford Appleton Laboratory (UK) is home to optical tweezers, femtosecond pump-probe spectroscopy, time-resolved stimulated and resonance Raman spectroscopy, time-resolved linear and non-linear infrared transient spectroscopy, to name just a few techniques [36]. 

Since there are a large number of different experimental laser and detection systems that can be used for time-resolved resonance Raman experiments, we shall only focus our attention here on two common types of methods that are typically used to investigate chemical reactions. We shall first describe typical nanosecond TR spectroscopy instrumentation that can obtain spectra of intermediates from several nanoseconds to millisecond time scales by employing electronic control of the pnmp and probe laser systems to vary the time-delay between the pnmp and probe pnlses. We then describe typical ultrafast TR spectroscopy instrumentation that can be used to examine intermediates from the picosecond to several nanosecond time scales by controlling the optical path length difference between the pump and probe laser pulses. In some reaction systems, it is useful to utilize both types of laser systems to study the chemical reaction and intermediates of interest from the picosecond to the microsecond or millisecond time-scales. 

Although very detailed, fundamental information is available from ultrafast TRIR methods, significant expertise in femtosecond/picosecond spectroscopy is required to conduct such experiments. TRIR spectroscopy on the nanosecond or slower timescale is a more straightforward experiment. Here, mainly two alternatives exist step-scan FTIR spectroscopy and conventional pump-probe dispersive TRIR spectroscopy, each with their own strengths and weaknesses. Commercial instruments for each of these approaches are currently available. 

Time-resolved spectroscopy is performed using a pump-probe method in which a short-pulsed laser is used to initiate a T-jump and a mid-IR probe laser is used to monitor the transient IR absorbance in the sample. A schematic of the entire instrument is shown in Fig. 17.4. For clarity, only key components are shown. In the description that follows, only those components will be described. A continuous-wave (CW) lead-salt (PbSe) diode laser (output power <1 mW) tuned to a specific vibrational mode of the RNA molecule probes the transient absorbance of the sample. The linewidth of the probe laser is quite narrow (<0.5 cm-1) and sets the spectral resolution of the time-resolved experiments. The divergent output of the diode laser is collected and collimated by a gold coated off-axis... 

Figure 5. Set of time-resolved UV-near-IR spectroscopic data (3.44-0.99 eV) following the femtosecond UV excitation of an aqueous sodium chloride solution ([H20]/[NaCl] = 55). An instrumental response of the pump-probe configuration at 1.77 eV (n-heptane) is also shown in the middle part of the figure. The ultra-short-lived components discriminated by UV and IR spectroscopy correspond to low or high excited CTTS states (CTTS, CTTS ), electron-atom pairs (Che pairs), and excited hydrated electrons (ehyd )- The spectral signature of relaxed electronic states (ground state of a hydrated electron, (ehyd) electron-cation pairs, a e hyd) observed in the red spectral region.

Fig. 7 X-ray photoelectron spectrometer. Left schematic view of a SSX 100/206 (Surface Science Instruments). Right, photographs of a Kratos Axis Ultra (Kratos Analytical) with the introduction and intermediate chambers (top) and analysis chamber (bottom), a, Turbomolecular pump b, cryogenic pump c, introduction chamber d, sample analysis chamber (SAC) e, transfer probe f, automatized X, Y, Z manipulator g, X-ray monochromator h, electrostatic lens i, hemispherical analyzer (HSA) j, ion gun k, aluminum anode (with monochromator) 1, aluminum-magnesium twin anode m, detector. Left channel plate. Right 8 channeltrons (Spectroscopy mode), phosphor screen behind a channel plate with a video camera (Imaging mode) n, spherical mirror analyzer (SMA) o, parking facility in the sample transfer chamber p, sample cooling device for the introduction chamber q, sample transfer chamber r, monitor interconnected with the video camera viewing samples in the SAC s, video camera in the SAC t, high temperature gas ceU (catalyst pretreatment)...

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