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Characterization of triplet states of axially symmetric benzenes using the zeeman effect

Hochstrasser, R. M. and Wessel, J. E. and Whiteman, J. D. and Zewail, A. H. (1971) Characterization of triplet states of axially symmetric benzenes using the zeeman effect. Chemical Physics Letters, 10 (4). pp. 452-454. ISSN 0009-2614. doi:10.1016/0009-2614(71)80332-9.

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By means of low temperature spectroscopy of single crystals of sym-trichlorobenzene (TCB) and sym-tribromobenzene (TBB) we have determined that the principal Herzberg-Teller origins in the S_0 → T_1 transition correspond to out-of-plane vibrations. The assigned active modes for TCB are: 205 cm^(−1) (e"), 144 cm^(−1) (a"2) from phosphorescence; 119 cm^(−1) (e" or a"2) from absorption. For TBB the assigned modes are: 203 cm^(−1) (e") from phosphorescence; 166, 207 cm^(−1) (e" or a"2) from absorption. The singlet-triplet transitions are dominated by these vibronic origins, and the electronic origins are relatively weak and manifest crystal field induced interactions as evidenced by the Zeeman effect analysis. The appearance of these low frequency out-of-plane modes indicates that the halogen atom motion induced mixing of the pi and sigma type electronic states is dominating the transition mechanism.

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Additional Information:© 1971 Elsevier B.V. Received 14 June 1971. This research was supported in part by a U.S. Department of Health Grant, GM 12592, and in part by the Advanced Research Projects Agency. We are indebted to the National Magnet Laboratory, M.I.T. for the use of their facilities in 1966 for the Zeeman work on TBB.
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NIHGM 12592
Advanced Research Projects Agency (ARPA)UNSPECIFIED
Issue or Number:4
Record Number:CaltechAUTHORS:20160929-124949627
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Official Citation:R.M Hochstrasser, J.E Wessel, J.D Whiteman, A.H Zewail, Characterization of triplet states of axially symmetric benzenes using the zeeman effect, Chemical Physics Letters, Volume 10, Issue 4, 15 August 1971, Pages 452-454, ISSN 0009-2614, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70665
Deposited By: Ruth Sustaita
Deposited On:30 Sep 2016 17:13
Last Modified:11 Nov 2021 04:33

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