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Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

Sahoo, Sangram Keshari and Umapathy, Siva and Parker, Anthony W (2011) Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates. In: Applied Spectroscopy, 65 (10). pp. 1087-1115.

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Abstract

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Society for Applied Spectroscopy.
Keywords: Time-resolved resonance Raman spectroscopy;TR3 spectroscopy; Quinones;Charge transfer complex;Photobiology;Isomerization; Inorganic complexes
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 04 Nov 2011 10:01
Last Modified: 04 Nov 2011 10:01
URI: http://eprints.iisc.ernet.in/id/eprint/41830

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