Light, intensity-modulated

The combination of photocurrent measurements with photoinduced microwave conductivity measurements yields, as we have seen [Eqs. (11), (12), and (13)], the interfacial rate constants for minority carrier reactions (kn sr) as well as the surface concentration of photoinduced minority carriers (Aps) (and a series of solid-state parameters of the electrode material). Since light intensity modulation spectroscopy measurements give information on kinetic constants of electrode processes, a combination of this technique with light intensity-modulated microwave measurements should lead to information on kinetic mechanisms, especially very fast ones, which would not be accessible with conventional electrochemical techniques owing to RC restraints. Also, more specific kinetic information may become accessible for example, a distinction between different recombination processes. Potential-modulation MC techniques may, in parallel with potential-modulation electrochemical impedance measurements, provide more detailed information relevant for the interpretation and measurement of interfacial capacitance (see later discus-... 

Light intensity modulation spectroscopy (IMPS) HinoA... 

Characterization of Electron Diffusion and Back-transfer by Light Intensity Modulated Techniques In Sect. 2.1.2, it was shown that time-resolved methods are required to obtain information on the kinetics and dynamics of a system. 

Hsu Tsung-Chun, Lu Ching-Heng, Huang Yu-Ting, et al. Concentric polymer-dispersed liquid crystal rings for light intensity modulation. Sensor. Actuat. A-Phys. 169 no. 2 (2011) 341-346. 

Figure 10-4. Transmitted light intensity modulated by the changes of optical retardation (top curve) vs. slowly changing voltage (bottom trace) applied at two different frequencies 100 kHz (left part) and IkHz (right part) to the MLC2048 cell of thickness d = 10 p.m. Point O corresponds to light transmittance at zero voltage. Reprinted with permission from Y. Yin, S. V. Shiyanovskii, A. B. Golovin and O. D. Lavrentovich, Phys. Rev. Lett, 95, 087801. Copyright (2006) by the American Physical Society...

On metals in particular, the dependence of the radiation absorption by surface species on the orientation of the electrical vector can be fiilly exploited by using one of the several polarization techniques developed over the past few decades [27, 28, 29 and 30], The idea behind all those approaches is to acquire the p-to-s polarized light intensity ratio during each single IR interferometer scan since the adsorbate only absorbs the p-polarized component, that spectral ratio provides absorbance infonnation for the surface species exclusively. Polarization-modulation mediods provide the added advantage of being able to discriminate between the signals due to adsorbates and those from gas or liquid molecules. Thanks to this, RAIRS data on species chemisorbed on metals have been successfidly acquired in situ under catalytic conditions [31], and even in electrochemical cells [32]. 

Light intensity and potential-modulated microwave measurements <5//. SDU—t Microwave impedance spectroscopy ... 

The reflectance, R, is defined as the ratio of the reflected light intensity to the intensity of the incident beam. Usually, one determines the change in reflectance, A/ , induced by some parameter, such as the electrode potential. Experimentally, one measures only the intensity of the reflected beam, 4. So if the incident intensity remains constant, the reflected beam gives hJl/R = A4/4. Experimental results are presented as plots of A/J/R vs. the parameter of interest, such as the frequency of the incident light or electrode potential. Modulation schemes, wherein the beam is chopped or the potential is modulated, are used to enhance the signal-to-noise ratio. 

With the resonance to the electronic transition, the ground-state population is partially depleted by the pump irradiation and restored with the time delay. The raw intensity of SH light was accordingly damped at fa = 0 and recovered in picoseconds, as seen in Figure 6.3a. Intensity modulation due to the vibrational coherence was superimposed on the non-modulated evolution as expected from Eq. (6.3). The coherence continued for picoseconds on this solution surface. The non-modulated component Isecond(fd> 2 ii) was fitted with a multiexponential... 

FIG. 66. Effects of modulating the RF excitation frequency (a) deposition rate and average light intensity as a function of the modulation frequency, with the deposition rate at cw conditions indicated by the dotted line, (b) measured spectrally integrated emission and calculated production of SiH3 radicals as a function of time, at a modulation frequency of 50 kHz and a 509f duty cycle. [From A. C. W. Biebericher. J, Bezemer. W. F. van der Weg, and W. J. Goedheer, Appl. Phys. Lett. 76, 2002 (2000), 2000, American Institute of Physics, w ith permission.]... 

Under potentiostatic conditions, the photocurrent dynamics is not only determined by faradaic elements, but also by double layer relaxation. A simplified equivalent circuit for the liquid-liquid junction under illumination at a constant DC potential is shown in Fig. 18. The difference between this case and the one shown in Fig. 7 arises from the type of perturbation introduced to the interface. For impedance measurements, a modulated potential is superimposed on the DC polarization, which induces periodic responses in connection with the ET reaction as well as transfer of the supporting electrolyte. In principle, periodic light intensity perturbations at constant potential do not affect the transfer behavior of the supporting electrolyte, therefore this element does not contribute to the frequency-dependent photocurrent. As further clarified later, the photoinduced ET... 

The basic experimental arrangements for photocurrent measurements under periodic square and sinusoidal light perturbation are schematically depicted in Fig. 19. In the previous section, we have already discussed experimental results based on chopped light and lock-in detection. This approach is particularly useful for measurement at a single frequency, generally above 5 Hz. At lower frequencies the performance of lock-in amplifier and mechanical choppers diminishes considerably. For rather slow dynamics, DC photocurrent transients employing optical shutters are more advisable. On the other hand, for kinetic studies of the various reaction steps under illumination, intensity modulated photocurrent spectroscopy (IMPS) has proved to be a very powerful approach [132,133,148-156]. For IMPS, the applied potential is kept constant and the light intensity is sinusoid-... 

FIG. 19 Block diagrams for photocurrent measurements with chopped light and lock-in detection (a) as well as for intensity-modulated photocurrent spectroscopy (b). (Adapted from Ref. 85.)... 

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