By George Porter (auth.), Kenneth B. Eisenthal (eds.)
With the advance of lasers that could generate mild eleven 14 pulses starting from 10- - 10- sec period, and in a position to thirteen height powers in far more than 10 watts scientists were in a position to examine the interactions of sunshine with subject in a time and gear area now not formerly attainable. those ultrashort laser pulses supply a strong software for the research of chemical phenomena on the so much basic point. a number of the uncomplicated approaches of value in chemistry together with power dissipa tion, molecular motions, structural and chemical alterations happen on a really couple of minutes scale and hence require detailed methods. Th~ use of ultrashort laser pulses to perturb and to probe platforms of curiosity offers an instantaneous method of the time reso lution of very fast chemical phenomena. It used to be attractiveness of the influence of those rather new ways to chemical phenomena that stimulated NATO to sponsor a gathering at the functions of picosecond spectroscopy in chemistry. the first goal of the NATO workshop was once to realize a few viewpoint at the prestige of the sector by way of current study actions, technological advancements and if attainable the tough activity of sensing destiny instructions. the best way we determined to strategy those matters was once to collect jointly the most participants to the sphere, thankfully a lot of whom have been in a position to attend, to provide their paintings and to take part in what grew to become out to be energetic discussions of the field.
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Additional resources for Applications of Picosecond Spectroscopy to Chemistry
Chern. Soc. 104, pp. 7191-7195. , Sakata, Y. and Misurni, S. 1981, J. Phys. Chern. 85, pp. 3957-3960. Mataga, N. and Tsuno, S. 1956, Naturwiss. 10, pp. 304-305. , Okada, T. and Mataga, N. 1981, Bull. Chern. Soc. Jpn. 54, pp. 1025-1030. Martin, M. , Okada, T. and Mataga, N. 1982, J. Phys. Chern. 86, 4148-4156. , Okada, T. , 1983, J. Am. Chern. , in press. Ikeda, N. , to be published. , Okada, T. , to be published. APPLICATION OF PICOSECOND SPECTROSCOPY TO ORGANIC REACTION MECHANISMS Kevin S. Peters Department of Chemistry, Harvard University INTODUCTION Organic reaction mechanisms are normally formulated in terms of bond rearrangements often without reference to the relevant time scale.
We note that Scheme 2 predicts that the excited triplet should undergo certain reactions that the ground triplet would not. , with alcohols. DPC was generated by UV laser_~rradiation of the precursor molecule diphenyldiazomethane (10 M) in a degassed acetonitrile solution. Excitation of the precursor molecule with a single laser pulse from a frequency quadrupled Nd:YAG laser (266 nm) produces STUDIES OF THE CHEMICAL INTERMEDIATE DIPHENYLCARBENE 53 two fragments, diphenylcarbene and N2 • A second UV laser pulse also at the same wavelength was time delayed by 8 ns after the first laser pulse and was used to excite the carbene fragment from its ground state, 3DPC, to its excited triplet state, 3*DPC.
This result can be explained by assuming non-parallel conformation of pyrene-NEA exciplex, where the N-H or N-D bond is almost perpendicular to the pyrene plane at C1 position and "hydrogen bonding" interaction between 2pnAO at C1 of the pyrene anion and N-H of NEA cation is responsible for keeping the oblique configuration of the exciplex (17). This oblique configuration is favorable not only for the proton transfer but also for the fast· ISC because of the enhancement of the spin-orbit interaction matrix element between the CT and the pyrene local triplet state in this configuration (7).