Ultrafast infra-red spectroscopy as a probe of chemical reaction mechanisms
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Ultrafast infra-red spectroscopy as a probe of chemical reaction mechanisms
Wed, 23/11/2016 - 16:00 to 17:00
Location:
Speaker:
Prof. Andrew Orr-Ewing
Affiliation:
University of Bristol
Synopsis:
The timescales for reactions in solution are very fast, with lifetimes of reactive intermediates that can be as short as a few picoseconds. Nevertheless, these intermediates can be observed, and the steps in photochemical reactions can be followed using techniques based on ultrafast infra-red spectroscopy. Two-dimensional infra-red spectroscopy (2DIR) provides further insights into structural changes and energy flow in molecules on these very short timescales. This talk will introduce the techniques of ultrafast time resolved infra-red and 2DIR spectroscopy and illustrate their application to the study of the mechanisms of chemical reactions. Examples will be drawn from our work on organic radical reactions in solution, photochemistry of DNA nucleobases, and isomerization dynamics in transition metal complexes.
Illustrative recent publications:
Ultraviolet absorption induces hydrogen-atom transfer in G-C Watson-Crick DNA base pairs in solution, K. Röttger, H.J.B. Marroux, M.P. Grubb, P.M. Coulter, H. Böhnke, A. Henderson, M.C. Galan, F. Temps, A.J. Orr-Ewing and G.M. Roberts, Angewandte Chemie 54, 14719 – 14722 (2015). DOI: 10.1002/anie.201506940
The study of reactive intermediates in condensed phases, B.K. Carpenter, J.N. Harvey and A.J. Orr-Ewing, J. Am. Chem. Soc. 138, 4695 – 4705 (2016). DOI: 10.1021/jacs.6b01761
Distinguishing population and coherence transfer pathways in a metal dicarbonyl complex using pulse-shaped 2DIR spectroscopy, H.J.B. Marroux and A.J. Orr-Ewing, J. Phys. Chem. B 120, 4125-4130 (2016). DOI: 10.1021/acs.jpcb.6b02979
Photochemical reaction dynamics of 2,2’-dithiobis(benzothiazole): direct observation of the addition product of an aromatic thiyl radical to an alkene with time-resolved vibrational and electronic absorption spectroscopy, D. Koyama and A.J. Orr-Ewing, PCCP 18, 12115-12127 (2016). DOI: 10.1039/C6CP01290F
Triplet state formation and quenching dynamics of 2-Mercaptobenzothiazole in solution, D. Koyama and A.J. Orr-Ewing, PCCP accepted for publication (2016). DOI: 10.1039/C6CP05110C