Electron time resolved

Petek H and Ogawa S 1997 Femtosecond time-resolved two-photon photoemission studies of electron dynamics in metals Prog. Surf. Sc/. 56 239... 

Many of the fiindamental physical and chemical processes at surfaces and interfaces occur on extremely fast time scales. For example, atomic and molecular motions take place on time scales as short as 100 fs, while surface electronic states may have lifetimes as short as 10 fs. With the dramatic recent advances in laser tecluiology, however, such time scales have become increasingly accessible. Surface nonlinear optics provides an attractive approach to capture such events directly in the time domain. Some examples of application of the method include probing the dynamics of melting on the time scale of phonon vibrations [82], photoisomerization of molecules [88], molecular dynamics of adsorbates [89, 90], interfacial solvent dynamics [91], transient band-flattening in semiconductors [92] and laser-induced desorption [93]. A review article discussing such time-resolved studies in metals can be found in... 

Fessenden R W and Verma N C 1976 Time resolved electron spin resonance spectroscopy. III. Electron spin resonance emission from the hydrated electron. Possible evidence for reaction to the triplet state J. Am. Chem. Soc. 98 243-4... 

Menetret J-F, Hofmann W, Schroder R R, Rapp G and Goody R S 1991 Time-resolved cryo-electron microscopic study of the dissociation of actomyosin Induced by photolysis of photolablle nucleotides J. Mol. Biol. 219 139-43... 

So far we have exclusively discussed time-resolved absorption spectroscopy with visible femtosecond pulses. It has become recently feasible to perfomi time-resolved spectroscopy with femtosecond IR pulses. Flochstrasser and co-workers [M, 150. 151. 152. 153. 154. 155. 156 and 157] have worked out methods to employ IR pulses to monitor chemical reactions following electronic excitation by visible pump pulses these methods were applied in work on the light-initiated charge-transfer reactions that occur in the photosynthetic reaction centre [156. 157] and on the excited-state isomerization of tlie retinal pigment in bacteriorhodopsin [155]. Walker and co-workers [158] have recently used femtosecond IR spectroscopy to study vibrational dynamics associated with intramolecular charge transfer these studies are complementary to those perfomied by Barbara and co-workers [159. 160], in which ground-state RISRS wavepackets were monitored using a dynamic-absorption technique with visible pulses. 

Hydrogen transfer in excited electronic states is being intensively studied with time-resolved spectroscopy. A typical scheme of electronic terms is shown in fig. 46. A vertical optical transition, induced by a picosecond laser pulse, populates the initial well of the excited Si state. The reverse optical transition, observed as the fluorescence band Fj, is accompanied by proton transfer to the second well with lower energy. This transfer is registered as the appearance of another fluorescence band, F2, with a large anti-Stokes shift. The rate constant is inferred from the time dependence of the relative intensities of these bands in dual fluorescence. The experimental data obtained by this method have been reviewed by Barbara et al. [1989]. We only quote the example of hydrogen transfer in the excited state of... 

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). 

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. 

However, time-resolved X-ray diffraction remains a young science. It is still impossible, or is at least very difficult, to attain time scales below to a picosecond. General characteristics of subpicosecond X-ray diffraction and absorption are hardly understood. To progress in this direction, free electron laser X-ray sources are actually under construction subject to heavy financial constraints. Nevertheless, this field is exceptionally promising. Working therein is a challenge for everybody ... 

C. H. Chao, S. H. Ein, W. K. Liu, and P. Rentzepis, Theory of ultrafast time-resolved X-ray and electron diffraction. In J. R. Helliwell and P. M. Rentzepis (eds.), Time-Resolved Diffraction, Volume 2 of Oxford Series on Synchrotron Radiation, Chap. 11, pp. 260-283. Oxford University Press, Oxford, 1997. 

BURNS c s, HEYERICK A, KEUKELEiRE D D and FOBES M D E (2001) Mechanism for formation of the light struck flavour in beer revealed by time-resolved electron paramagnetic resonance, Chem Eur J, 7, 4554-61. 

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