Time dependent absorption optical spectroscopy

Finally, forward ISRS excitation can be followed by measurement of time-dependent absorption or Raman spectra, second harmonic generation efficiency, or any other optical property that may be affected by vibrational distortion. Preliminary time-resolved absorption spectroscopy of nonequilibrium, vibrationally distorted species is discussed further in the next section [46]. 

One interesting new field in the area of optical spectroscopy is near-field scaiming optical microscopy, a teclmique that allows for the imaging of surfaces down to sub-micron resolution and for the detection and characterization of single molecules [, M]- Wlien applied to the study of surfaces, this approach is capable of identifying individual adsorbates, as in the case of oxazine molecules dispersed on a polymer film, illustrated in figure Bl.22,11 [82], Absorption and emission spectra of individual molecules can be obtamed with this teclmique as well, and time-dependent measurements can be used to follow the dynamics of surface processes. 

Transient terahertz spectroscopy Time-resolved terahertz (THz) spectroscopy (TRTS) has been used to measure the transient photoconductivity of injected electrons in dye-sensitised titanium oxide with subpicosecond time resolution (Beard et al, 2002 Turner et al, 2002). Terahertz probes cover the far-infrared (10-600 cm or 0.3-20 THz) region of the spectrum and measure frequency-dependent photoconductivity. The sample is excited by an ultrafast optical pulse to initiate electron injection and subsequently probed with a THz pulse. In many THz detection schemes, the time-dependent electric field 6 f) of the THz probe pulse is measured by free-space electro-optic sampling (Beard et al, 2002). Both the amplitude and the phase of the electric field can be determined, from which the complex conductivity of the injected electrons can be obtained. Fitting the complex conductivity allows the determination of carrier concentration and mobility. The time evolution of these quantities can be determined by varying the delay time between the optical pump and THz probe pulses. The advantage of this technique is that it provides detailed information on the dynamics of the injected electrons in the semiconductor and complements the time-resolved fluorescence and transient absorption techniques, which often focus on the dynamics of the adsorbates. A similar technique, time-resolved microwave conductivity, has been used to study injection kinetics in dye-sensitised nanocrystalline thin films (Fessenden and Kamat, 1995). However, its time resolution is limited to longer than 1 ns. 

The relationship between the structure of a polymer chain and it dynamics has long been a focus for work in polymer science. It is on the local level that the dynamics of a polymer chain are most directly linked to the monomer structure. The techniques of time-resolved optical spectroscopy provide a uniquely detailed picture of local segmental motions. This is accomplished through the direct observation of the time dependence of the orientation autocorrelation function of a bond in the polymer chain. Optical techniques include fluorescence anisotropy decay experiments (J ) and transient absorption measurements(7 ). A common feature of these methods is the use of polymer chains with chromophore labels attached. The transition dipole of the attached chromophore defines the vector whose reorientation is observed in the experiment. A common labeling scheme is to bond the chromophore into the polymer chain such that the transition dipole is rigidly affixed either para 1 lei (1-7) or perpendicular(8,9) to the chain backbone. 

Picosecond absorption spectroscopy has been employed to follow the time-dependence of the optical absorption during the formation of e, while pulsed-laser saturation spectroscopy has been used to examine the... 

The basic scheme adapted for generating 2D IR spectra [3, 8] is shown in Figure 1-2. In a typical optical spectroscopy experiment, an electromagnetic probe (e.g., IR, X-ray, UV or visible light) is applied to the system of interest, and physical or chemical information about the system is obtained in the form of a spectrum representing a characteristic transformation (e.g., absorption, retardation, and scattering) of the electromagnetic probe by the system constituents. In a 2D IR experiment, an external physical perturbation is applied to the system [2, 3] with the incident IR beam used as a probe for spectroscopic observation. Such a perturbation often induces time-dependent fluctuations of the spectral intensity, toown as the dynamic spectrum, superposed onto the normal static IR spectrum. 

In this chapter, we focus on the most important methodological features of the vibrational and electronic treatment by a time-dependent approach. Then, we give a brief sketch of the nonperiodic GLOB model. A list of illustrative applications is discussed in Section 11.3. Regarding the IR and vibrational analysis, we choose two important benchmark systems for the polypeptides and ions in solution, namely, A-methyl-acetamide and Zn(II) in aqueous solution. Further, optical absorption spectra are illustrated for a solvatochromic shift prototype of the carbonyl n —> ti transition (acrolein) and for an extended system, such as liquid water. Finally, we consider the characterization of the phosphorescence emission spectroscopy involving the acetone molecule in the electronic triplet state. Concluding remarks and perspectives are sketched in Section 11.4. 

Another important aspect about the optical properties of QDs is the multiphoton process which has been widely applied in recent years in biological and medical imaging after the pioneer work of Goeppert-Mayer (1931), Lami et al. (1996), Helmchen et al. (1996), Yokoyama et al. (2006). The multiphoton process has largely been treated theoretically by steady-state perturbation approaches, for example, the scaling rules of multiphoton absorption by Wherrett (1984) and the analysis of two-photon excitation spectroscopy of CdSe QDs by Schmidt et al. (1996). Non-perturbation time-dependent Schrodinger equation was solved to analyze the ultrafast (fs) and ultra-intense (in many experiments the optical power of laser pulse peak can reach... 

A useful and common way of describing the reorientation dynamics of molecules in the condensed phase is to use single molecule reorientation correlation functions. These will be described later when we discuss solute molecular reorientational dynamics. Indirect experimental probes of the reorientation dynamics of molecules in neat bulk liquids include techniques such as IR, Raman, and NMR spectroscopy. More direct probes involve a variety of time-resolved methods such as dielectric relaxation, time-resolved absorption and emission spectroscopy, and the optical Kerr effect. The basic idea of time-resolved spectroscopic techniques is that a short polarized laser pulse removes a subset of molecular orientations from the equifibrium orientational distribution. The relaxation of the perturbed distribution is monitored by the absorption of a second time-delayed pulse or by the time-dependent change in the fluorescence depolarization. 

---