Time resolved optical response

Other Work on Water-Related Systems. Sonoda et al.61 have simulated a time-resolved optical Kerr effect experiment. In this model, which uses molecular dynamics to represent the behaviour of the extended medium, the principle intermolecular effects are generated by the dipole-induced-dipole (DID) mechanism, but the effect of the second order molecular response is also include through terms involving the static molecular / tensor, calculated by an MP2 method. Weber et al.6S have applied ab initio linear scaling response theory to water clusters. Skaf and Vechi69 have used MP2/6-311 ++ G(d,p) calculation of the a and y tensors of water and dimethylsulfoxide (DMSO) to carry out a molecular dynamics simulation of DMSO/Water mixtures. Frediani et al.70 have used a new development of the polarizable continuum model to study the polarizability of halides at the water/air interface. 

The subpicosecond time-resolved optical Kerr effect was used to determine the nonresonant optical nonlinearity. A power law dependence of the second-order hyperpolarizability y, of the polybenzonitrile molecule on the average degree of polymerization was discussed. Based on the transient response, which was primarily pulse limited, the relaxation time of the samples was shorter than the laser pulse width. 

The above theory is usually called the generalized linear response theory because the linear optical absorption initiates from the nonstationary states prepared by the pumping process [85-87]. This method is valid when pumping pulse and probing pulse do not overlap. When they overlap, third-order or X 3 (co) should be used. In other words, Eq. (6.4) should be solved perturbatively to the third-order approximation. From Eqs. (6.19)-(6.22) we can see that in the time-resolved spectra described by x"( ), the dynamics information of the system is contained in p(Af), which can be obtained by solving the reduced Liouville equations. Application of Eq. (6.19) to stimulated emission monitoring vibrational relaxation is given in Appendix III. 

Fig. 3.5. Experimental apparatus for time-resolved THz transmission spectroscopy. The sample is excited with a visible laser pulse delivered by delay line 3. A singlecycle THz electric-field transient probes the polarization response of the sample after time delay tv scanned by delay line 1. The transmitted THz amplitude is monitored via ultrabroadband electro-optic sampling in a THz receiver as a function of time T scanned by delay line 2. From [13]...

Photodiodes occur in many different varieties and are useful in both steady-state and time-resolved fluorescence studies. Photodiodes designed for use in steady-state or on microsecond time-scales are inexpensive and have effective areas up to a few square millimeters, and are capable of efficiently matching to simple focusing optics. However, as the temporal resolution increases so does the cost, and the effective area has to be reduced. For example, APDs with response times in the 50 psec region have effective diameters ofca. 10 /small active area of high-speed devices is currently the primary drawback in fluorescence studies. Also, photodiodes other... 

The most convenient means of making time-resolved SH measurements on metallic surfaces is to use a cw laser as a continuous monitor of the surface during a transient event. Unfortunately, in the absence of optical enhancements, the signal levels are so low for most electrochemical systems that this route is unattractive. A more viable alternative is to use a cw mode-locked laser which offers the necessary high peak powers and the high repetition rate. The experimental time resolution is typically 12 nsec, which is the time between pulses. A Q-switched Nd YAG provides 30 to 100 msec resolution unless the repetition rate is externally controlled. The electrochemical experiments done to date have involved the application of a fast potential step with the surface response to this perturbation followed by SHG [54, 55,116, 117]. Since the optical technique is instantaneous in nature, one has the potential to obtain a clearer picture than that obtained by the current transient. The experiments have also been applied to multistep processes which are difficult to understand by simple current analysis [54, 117]. 

The time-resolved photoconductivity measurements shown in Fig. 15 give further support for a difference in the photoinduced charge transport in the polymerized samples versus the unpolymerized samples. For the incident laser of 100 mW/cm2 and a spot size of 2.5 mm, the decay time of the photoconductivity for the unpolymerized samples is 7.4 sec, whereas the photoconductivity of the polymerized samples does not significantly drop over a 30 sec period. Also, the photoconductivity of the polymerized sample is nearly twice that of the unpolymerized samples even at the peak of the unpolymerized photoconductive response. The unnormalized values for the dark conductivity in both samples is 1.7 x 10-10 S cm-1. The photoconductivity is 5.8 x 10-11 S cm-1 for the unpolymerized sample and 1.1 x 10-10 S cm-1 for the PSLC at an optical intensity of 2 W cm-2. 

As can be seen from Eq. (4.52), the dynamics of both population (i.e., time-resolved measurement and Eq. (4.52) can be applied to optical absorption and stimulated emission (SE). Furthermore, the ordinary linear response theory is recovered when au> — 0 and cru represents the Boltzmann distribution. 

The experimental techniques adopted to measure linear and nonlinear optical properties are quite different and must be discussed separately. In broad terms, linear properties can be measured using low intensity probes and high spectral resolution. They are usually understood in the frequency domain. Nonlinear responses on the contrary need very large intensities, typically achieved in short pulses, and are discussed in the time domain. In addition to these physical considerations, we have to remember that time-resolved spectroscopy and optical characterization usually require good optical quality samples, so our understanding of the physics of these materials is closely linked to their quality. 

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