Scherer, N. F. and Khundkar, L. R. and Rose, T. S. and Zewail, A. H. (1987) Sub-Doppler measurement of excited-state rotational constants and rotational coherence by picosecond multiphoton ionization mass spectrometry. Journal of Physical Chemistry, 91 (26). pp. 6478-6483. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20160906-090611093
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Abstract
A method is presented here for one-photon sub-Doppler measurement of excited-state rotational constants and coherence of large polyatomic molecules. The method, which relies on the concept of purely rotational coherence in molecules, utilizes (polarized) picosecond pumpprobe multiphoton ionization (MPI) mass spectrometry. It offers improved temporal resolution (pulse width limited) and is applicable to weakly or nonfluorescing molecules. The present implementation in a molecular beam provides measurements of the rotational constants in the excited (SI) state of trans-stilbene and gives information on the direction of the relevant transition moments involved. From the coherence decay of the initially prepared state we obtain the dephasing time, which we discuss in relation to experiments involving vibrational/rotational energy redistribution.
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| Additional Information: | © 1987 American Chemical Society. Received: September 3, 1987. We thank Mr. Spencer Baskin and Dr. Peter Felker for enlightening discussions. The computer simulation done here benefited from these discussions and from the work presented in ref 1 and 2. This work was supported by a grant from the National Science Foundation (DMR-8521191). | |||||||||
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| Issue or Number: | 26 | |||||||||
| Record Number: | CaltechAUTHORS:20160906-090611093 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20160906-090611093 | |||||||||
| Official Citation: | Sub-Doppler measurement of excited-state rotational constants and rotational coherence by picosecond multiphoton ionization mass spectrometry N. F. Scherer, L. R. Khundkar, T. S. Rose, and A. H. Zewail The Journal of Physical Chemistry 1987 91 (26), 6478-6483 DOI: 10.1021/j100310a012 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 70165 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 08 Sep 2016 18:42 | |||||||||
| Last Modified: | 03 Oct 2019 10:28 |
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