Time-Resolved Optical

Lantz J M and Corn R M 1994 Time-resolved optical second harmonic generation measurements of picosecond band flattening processes at single crystal TiO, electrodes J. Phys. Chem. 98 9387-90... 

Several strategies commonly used for time resolved optical absorjition spectroscopy (TROA) are shown... 

Figure C3.1.7. Time-resolved optical absorjDtion data for the Soret band of photo lysed haemoglobin-CO showing six first-order (or pseudo-first-order) relaxation phases, I-VI, on a logaritlimic time scale extending from nanoseconds to seconds. Relaxations correspond to geminate and diffusive CO rebinding and to intramolecular relaxations of tertiary and quaternary protein stmcture. (From Goldbeck R A, Paquette S J, Bjorling S C and Kliger D S 1996 Biochemistry 35 8628-39.)...

Bruckner V, Feller K-H and Grummt U-W 1990 Applications of Time-Resolved Optical Spectroscopy (New York Elsevier)... 

A comprehensive review of fast and ultrafast time-resolved optical techniques. 

Time-resolved optical absorption spectroscopy experiments have shown that arenesul-fonyl radicals decay with clean second-order kinetics14 the values of 2 k,/a h where s2 is the extinction coefficient at the monitoring wavelength, increased linearly with decreasing viscosity of the solvent, further indicating that reaction 16 is clearly a diffusion-controlled process. 

Cluster Fx was also identified via its EPR spectral features in the RCI photosystem from green sulfur bacteria 31, 32) and the cluster binding motif was subsequently found in the gene sequence 34 ) of the (single) subunit of the homodimeric reaction center core (for a review, see 54, 55)). Whereas the same sequence motif is present in the RCI from heliobacteria (50), no EPR evidence for the presence of an iron-sulfur cluster related to Fx has been obtained. There are, however, indications from time-resolved optical spectroscopy for the involvement of an Fx-type center in electron transfer through the heliobacterial RC 56). 

The first theoretical attempts in the field of time-resolved X-ray diffraction were entirely empirical. More precise theoretical work appeared only in the late 1990s and is due to Wilson et al. [13-16]. However, this theoretical work still remained preliminary. A really satisfactory approach must be statistical. In fact, macroscopic transport coefficients like diffusion constant or chemical rate constant break down at ultrashort time scales. Even the notion of a molecule becomes ambiguous at which interatomic distance can the atoms A and B of a molecule A-B be considered to be free Another element of consideration is that the electric field of the laser pump is strong, and that its interaction with matter is nonlinear. What is needed is thus a statistical theory reminiscent of those from time-resolved optical spectroscopy. A theory of this sort was elaborated by Bratos and co-workers and was published over the last few years [17-19]. 

In the previous Maxwelhan description of X-ray diffraction, the electron number density n(r, t) was considered to be a known function of r,t. In reality, this density is modulated by the laser excitation and is not known a priori. However, it can be determined using methods of statistical mechanics of nonlinear optical processes, similar to those used in time-resolved optical spectroscopy [4]. The laser-generated electric field can be expressed as E(r, t) = Eoo(0 exp(/(qQr ot)), where flo is the optical frequency and q the corresponding wavevector. The calculation can be sketched as follows. 

Measurements of the lifetimes of NIESST states by time-resolved MES [51] and of LIESST states by time-resolved optical spectroscopy [52] on the very same system (a single crystal of [FC , Mni , (bpy)3] (bpy = bipyridine)) gave similar results. This supports the suggestion that the mechanisms for LIESST and NIESST relaxation are very similar, at least for the low-energy regime. The NIESST effect was also studied in Co(ll) SCO compounds, viz. [ Co/Co(terpy)2]X2 H20 (X = [CIOJ, n = V2,X = Cl , n = 5), where terpy is the tridentate ligand terpyridine... 

The radical cations of urazole-annelated azoalkanes 65 were generated by pulse radiolysis and the transients characterized spectrally and kinetically by time-resolved optical monitoring. The initial distonic 1,3 radical cations 66 were detected, and the methyl-substituted 66 further deprotonates to radical 67 (Scheme 1) <1997JA10673>. 

The reaction of thermally and photochemically generated tert-butoxyl radicals with trisubstituted silanes [Eqs. (6) and (7)] has been used extensively for the generation of silyl radicals in ESR studies, in time-resolved optical techniques, and in organic synthesis. Absolute rate constants for reaction (7) were measured directly by LFP techniques,56,62,63 whereas the gas phase kinetic values for reactions of Me3SiH were obtained by competition with decomposition of the tert-butoxyl radical.64,65... 

V. Jagannadham and S. Steenken, J. Amer. Chem. Soc. 106, 6542 (1984). The reaction of RCHOH, generated by pulse radiolysis, was studied with p-substituted nitrobenzenes using time-resolved optical and conductance detection. The radical anion of the nitrobenzene is produced directly and indirectly. 

The reaction of thermally and photochemically generated tcrt-butoxyl radicals with silicon hydrides (Reactions 3.13 and 3.14) has been extensively used for the generation of silyl radicals in EPR studies, time-resolved optical techniques, and organic synthesis. 

However, atom motions cannot be unambiguously imaged by time-resolved optical spectroscopic methods as they do not directly measure the structural dynamics but instead characterize energetic properties. Consequently, novel methods that enable the direct measurement of molecular motions during chemical processes are needed. Furthermore, chemical reactions often occur in solution and, consequently, it is desirable that such methods are applicable to chemical processes in the liquid phase. 

Langof, L. Ehrenfreund, E. Lifshitz, E. Continuous-Wave and Time-Resolved Optically Detected Magnetic Resonance Studies of Nonetched/Etched InP Nanocrystals. J. Phys. Chem. B 2002, 106, 1606-1612. 

Actually, the kinetic study of the cluster redox potential by pulse radiolysis [31] (Section 20.3.2) somewhat mimics the process of the black-and-white photographic development, except that clusters are free in the solution (not fixed on AgBr crystals), and that they are produced by ionizing radiation (as in radiography and not by visible photons but the last choice had been incompatible with the time-resolved optical detection in the visible. Beyond the critical nuclearity, they receive electrons without delay from the developer already present (actually, the photographic development is achieved in a delayed step). 

M = (Mx,My,M ) is the dipole moment of the system. Moreover, the indices i, j designate the Cartesian components x, y, z of these vectors, ()q realizes an averaging over all possible realizations of the optical field E, and () realizes an averaging over the states of the nonperturbed liquid sample. Two three-time correlation functions are present in Eq. (4) the correlation function of E(t) and the correlation function of the variables/(q, t), M(t). Such objects are typical for statistical mechanisms of systems out of equilibrium, and they are well known in time-resolved optical spectroscopy [4]. The above expression for A5 (q, t) is an exact second-order perturbation theory result. 

In some systems, triplet BET can occur, as deduced from time-resolved optical spectroscopy, magnetic field effects, CIDNP, or optoacoustic calorimetry. Triplet BET is governed by energetic factors, which determine rates, and by the relative topologies of the potential surfaces of parent molecule, radical ions, and of accessible triplet or biradical states. Divergent topologies for different states may cause rearrangements. 

The lifetime of the RSSR radical anions is usually very short on the microsecond timescale in water. However, they have been detected and characterized by time-resolved optical methods. In one early study, y irradiation of matrices containing alkyl and aryl disulfides provided spectroscopic evidence for the formation of the corresponding radical anions. Subsequently, the formation of RSSR radical anions has been well documented, particularly by EPR, flash photolysis, and pulse radiolysis. In fact, 2a/ a three-electron bonded radical anion species, particularly from sulfur compounds, constitute significant and interesting intermediates. The RSSR radical anions may be obtained from different approaches. One is by one-electron reduction of disulfides (equation 75), such as by pulse radiolysis. However, the most common approach is by association of RS and RS (equation 79). ... 

Giraud, G., Gordon, C. M., Dunkin, 1. R., and Wynne, K., The effects of anion and cation substitution on the ultrafast solvent dynamics of ionic liquids A time-resolved optical Kerr-effect spectroscopic study, /. Chem. Phys., 119,464-477,2003. 

Spoler, F, Frentz, M., Forst, M., Kurz, H., Schrage, N.F Analysis of hydrofluoric acid penetration and decontamination of the eye by means of time-resolved optical coherence tomography. Bums 34(4), 549-555 (2008). Epub 2007 Sep 14... 

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