Broadband pump-probe spectroscopy

A detailed description of experimental setup of the femtosecond broadband pump-probe spectroscopy was given in Ref [11, 16]. Schematic representation of the experimental setup is shown in Figure 11.3. The combination of femtosecond broadband pump-probe spectroscopy, with an expanded spectral range, and picosecond fluorescence decay measurements permitted more detailed analysis of electron transfer dynamics [17-19]. The authors disentangled the various kinetic... 

The mechanism and dynamics of photoinduced charge separation and charge recombination have been investigated in synthetic DNA hairpins possessing donor and acceptor stilbenes (stilbene-4,4 -dicarboxylic acid, bis(3-hydroxypropyl)amide of stilbene-4,4 -dicarboxylic acid, bis(2-hydroxyethyl)stilbene 4,4 -diether) (Figure 11.1) using femtosecond broadband pump-probe spectroscopy, nanosecond transient absorption spectroscopy, and picosecond fluorescence decay measurements [11]. Nanosecond time-resolved spectra of stilbenes attached to DNA are shown in Figure 11.4. 

In order to learn about the true quantum efficiency of photogeneration one therefore has to study the photoinduced charge generation mechanism at faster time scales. Pump probe spectroscopy utilising a few optical-cycle laser pulses (5-6 fs) in the visible spectral range with broadband frequency conversion techniques [89] now makes it possible to study extremely fast optically-initiated events with unprecedented time resolution. Such a setup was used to time-resolve the kinetics of the charge transfer process from a polymer chain to a fullerene moiety in thin films of poly[2-methoxy, 5-(3, 7 -dimethyl-octyloxy)]-p-phenylene vinylene (MDMO-PPV) and [6,6]-phenyl C6i butyric acid methyl ester (PCBM). Solutions prepared from 1 wt% solutions of toluene on thin quartz substrates were studied. 

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. 

A short pump pulse excites coherently different upper levels. The time evolution of the superposition of states following the coherent excitation causes time-dependent changes of the complex susceptibility x of the sample. Similar to the quantum beats in the fluorescence intensity the susceptibility x(t) is found to contain oscillating nonisotropic contributions which can be readily detected by placing the sample between crossed polarizers and transmitting a probe pulse with variable delay (see also Sect.10.3 on polarization spectroscopy). Even a cw broadband dye laser can be used for probing if the probe intensity transmitted by the polarizer is monitored with sufficient time resolution. 

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