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Doppler-free time-resolved polarization spectroscopy of large molecules: Measurement of excited state rotational constants

Baskin, J. S. and Felker, P. M. and Zewail, A. H. (1986) Doppler-free time-resolved polarization spectroscopy of large molecules: Measurement of excited state rotational constants. Journal of Chemical Physics, 84 (8). pp. 4708-4710. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:BASjcp86a

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Abstract

Measurement of the rotational spectra and constants of molecules can be a powerful probe of excited state geometries and intramolecular dynamics. The conventional approach for obtaining rationally resolved spectra is to use high-resolution (frequency domain, time-integrated) laser excitation. For medium-sized molecules, recent advances in these high-resolution techniques have made it possible to obtain Doppler-free spectra of benzene(1) (using two-photon excitation), and jet-cooled spectra of tetrazines,(2) pyrazine,(3) and others.(4) These results on medium-sized molecules have provided valuable information on geometries, (1,2) and on the dynamics of intramolecular singlet-triplet coupling(3,5) and the “channel 3” decay in benzene.(1) For large molecules, to obtain rationally resolved spectra one needs stable, ultra-narrow bandwidth lasers together with a scheme to reduce Doppler broadening to less than several megahertz.


Item Type:Article
Additional Information:Copyright © 1986 American Institute of Physics. Received 7 January 1986; accepted 6 February 1986. Arthur Amos Noyes Laboratory of Chemical Physics Contribution No. 7351. This work was supported by a grant from the National Science Foundation (DMR-8521191).
Subject Keywords:ROTATIONAL STATES; EXCITED STATES; ENERGY–LEVEL TRANSITIONS; POLARIZATION; SPECTRAL RESOLUTION; STILBENE; FLUORESCENCE; MOLECULAR STRUCTURE
Record Number:CaltechAUTHORS:BASjcp86a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:BASjcp86a
Alternative URL:http://dx.doi.org/10.1063/1.449998
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:2056
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Mar 2006
Last Modified:26 Dec 2012 08:47

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