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Determination of excited-state rotational constants and structures by Doppler-free picosecond spectroscopy

Baskin, J. Spencer and Zewail, Ahmed H. (1989) Determination of excited-state rotational constants and structures by Doppler-free picosecond spectroscopy. Journal of Physical Chemistry, 93 (15). pp. 5701-5717. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20160902-105850952

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Abstract

Picosecond time-resolved fluorescence measurement of purely rotational coherence is developed as a Doppler-free technique for the determination of rotational constants of large molecules in their excited states. We present detailed analyses of purely rotational coherence measurements, supplying new information about the rotational constants and structures of the first excited electronic states of t-stilbene, four t-stilbene van der Waals complexes, and anthracene, including values for all three anthracene S_1 rotational constants. Evidence is considered in the case of stilbene for a transition dipole with a significant component perpendicular to the a inertial axis, and the consequences of such a dipole are explored by way of numerical simulations. Excited-state structures are proposed for stilbene and stilbene-rare-gas complexes and comparisons made with model calculations of the van der Waals potential. Application of the new spectroscopic technique to molecules of large asymmetry is demonstrated by the analysis of fluorene and fluorene-argon measurements, and the results are compared with data from previously published high-resolution frequency domain studies.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j100352a014DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100352a014PublisherArticle
Additional Information:© 1989 American Chemical Society. Received: January 23, 1989. Publication Date: July 1989. This research was supported by a grant from the National Science Foundation (DMR-8521191).
Funders:
Funding AgencyGrant Number
NSFDMR-8521191
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics7747
Record Number:CaltechAUTHORS:20160902-105850952
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160902-105850952
Official Citation:Determination of excited-state rotational constants and structures by Doppler-free picosecond spectroscopy J. Spencer Baskin and Ahmed H. Zewail The Journal of Physical Chemistry 1989 93 (15), 5701-5717 DOI: 10.1021/j100352a014
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70149
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 Sep 2016 20:02
Last Modified:02 Sep 2016 20:02

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