Ultrafast Transient Absorption Spectroscopy

Alfano, J. C., Walhout, P. K., Kimura, Y. and Barbara, P. F. Ultrafast transient-absorption spectroscopy of the aqueous solvated electron, J.Chem.Phys., 98 (1993), 5996-5998... 

The dynamics of the interfacial electron-transfer between Dye 2 and TiOz were examined precisely by laser-induced ultrafast transient absorption spectroscopy. Durrant et al.38) employed subpicosecond transient absorption spectroscopy to study the rate of electron injection following optical excitation of Dye 2 adsorbed onto the surface of nanocrystalline Ti02 films. Detailed analysis indicates that the injection is at least biphasic, with ca. 50% occurring in <150 fsec (instrument response limited) and 50% in 1.2 0.2 psec. 

Kimura Y, Alfano JC, Walhout PK, Barbara PF (1994) Ultrafast transient absorption spectroscopy of the solvated electron in water. J Phys Chem 98 3450-3458 Li X, Sevilla MD, Sanche L (2003) Density functional theory studies of electron interaction with DNA can zero eV electrons induce strand breaks J Am Chem Soc 125 13668-13699 Lind J, Shen X, Eriksen TE, Merenyi G, Eberson L (1991) One-electron reduction of N-bromosuccin-imide. Rapid expulsion of a bromine atom. J Am Chem Soc 113 4629-4633 Marasas RA, lyoda T, Miller JR (2003) Benzene radical ion in equilibrium with solvated electrons. J Phys Chem A 107 2033-2038... 

The photodissociation of bromobenzene in solution has been investigated with ultrafast transient absorption spectroscopy, following excitation at 266 nm. The main kinetic feature in acetonitrile was a 9 ps decay that was assigned to predissociation similar decays were observed in hexane, dichloromethane and tetrachloromethane. Laser-aligned iodobenzene have been photodissociated into phenyl radicals and iodine atoms with a 1.5 ps laser pulse at 266 nm, and the yield of iodine photoproducts detected by resonant multiphoton ionization." Significant yield enhancements were observed when the dissociation laser was polarized parallel instead of perpendicular to the alignment laser polarization. 

Molecular dyads of ruthenium(ii)- or osmium(ii)-bis(terpyridine) chromophores and expanded pyridinium acceptors have been used to demonstrate the effect of the bridge and the metal ions to the photophysical properties of linear systems. In particular, via ultrafast transient absorption spectroscopy, an equilibration between MLCT and photo-induced charge-separated excited states has been observed demonstrating that intramolecular photoinduced electron transfers can occur within multicomponent systems in spite of driving forces virtually approaching zero. ... 

The long triplet lifetimes are attributed to reversible triplet energy transfer with the appended pyrene moieties and, using ultrafast transient absorption spectroscopy, the rates of formation of the equilibrium distribution of triplet states were determined [188]. 

The next two chapters are devoted to ultrafast radiationless transitions. In Chapter 5, the generalized linear response theory is used to treat the non-equilibrium dynamics of molecular systems. This method, based on the density matrix method, can also be used to calculate the transient spectroscopic signals that are often monitored experimentally. As an application of the method, the authors present the study of the interfadal photo-induced electron transfer in dye-sensitized solar cell as observed by transient absorption spectroscopy. Chapter 6 uses the density matrix method to discuss important processes that occur in the bacterial photosynthetic reaction center, which has congested electronic structure within 200-1500cm 1 and weak interactions between these electronic states. Therefore, this biological system is an ideal system to examine theoretical models (memory effect, coherence effect, vibrational relaxation, etc.) and techniques (generalized linear response theory, Forster-Dexter theory, Marcus theory, internal conversion theory, etc.) for treating ultrafast radiationless transition phenomena. 

Transient intermediates are most commonly observed by their absorption (transient absorption spectroscopy see ref. 185 for a compilation of absorption spectra of transient species). Various other methods for creating detectable amounts of reactive intermediates such as stopped flow, pulse radiolysis, temperature or pressure jump have been invented and novel, more informative, techniques for the detection and identification of reactive intermediates have been added, in particular EPR, IR and Raman spectroscopy (Section 3.8), mass spectrometry, electron microscopy and X-ray diffraction. The technique used for detection need not be fast, provided that the time of signal creation can be determined accurately (see Section 3.7.3). For example, the separation of ions in a mass spectrometer (time of flight) or electrons in an electron microscope may require microseconds or longer. Nevertheless, femtosecond time resolution has been achieved,186 187 because the ions or electrons are formed by a pulse of femtosecond duration (1 fs = 10 15 s). Several reports with recommended procedures for nanosecond flash photolysis,137,188-191 ultrafast electron diffraction and microscopy,192 crystallography193 and pump probe absorption spectroscopy194,195 are available and a general treatise on ultrafast intense laser chemistry is in preparation by IUPAC. 

The importance of carotenoids in photobiology is well known and there is a continuing interest in their photochemistry. Although they do not normally participate in PET processes because of the short lifetimes of their singlet states, incorporation into organized systems with suitable electron acceptors can lead to photoactivity. The dynamics of photoinduced electron injection and recombination between all-trans-8 -apo-p-caroten-8 -oic acid (125) and a Ti02 colloidal nanoparticle have been studied by means of transient absorption spectroscopy. " " An ultrafast ( 360 fs) electron injection from the initially excited S2 state of the carotenoic acid into the Ti02 conduction band with a quantum... 

Negrerie, M. Cianetti, S. Vos, M. H. Martin, J.-L. Kruglik, S. G., Ultrafast heme dynamics in ferrous versus ferric cytochrome c studied by time-resolved resonance Raman and transient absorption spectroscopy. J. Phys. Chem. B 2006, 110, 12766-12780. 

Kennis, J.T.M., Larsen, D.S., Ohta, K., Facciotti, M.T., Glaeser, R.M., et al. Ultrafast protein dynamics of bacteriorhodopsin probed by photon echo and transient absorption spectroscopy. J. Phys. Chem. B 106, 6067-6080 (2002)... 

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