Jet-cooled fluorescence spectra, Raman spectra, and potential energy surfaces of stilbenes

Jaan Laane; W.-Y. Chiang; K. Haller; A. del Rosario

doi:10.1117/12.220863

18 September 1995 Jet-cooled fluorescence spectra, Raman spectra, and potential energy surfaces of stilbenes

Jaan Laane, W.-Y. Chiang, K. Haller, A. del Rosario

Proceedings Volume 2548, Laser Techniques for State-Selected and State-to-State Chemistry III; (1995) https://doi.org/10.1117/12.220863
Event: SPIE's 1995 International Symposium on Optical Science, Engineering, and Instrumentation, 1995, San Diego, CA, United States

Abstract

The jet-cooled fluorescence excitation spectra and dispersed fluorescence spectra of trans- stilbene (t-S) and 4-methoxy-trans-stilbene (MS) have been recorded and analyzed. Preliminary results for 4,4'-dimethyl-trans-stilbene have also been obtained. The high- temperature vapor-phase and liquid phase Raman spectra of these molecules along with cis- stilbene have also been recorded. The low-frequency vibrational modes have been assigned, and the vibrational progressions associated with the two phenyl torsions and the ethylinic internal rotation, which primarily governs the photoisomerization process, have been analyzed. For t-S and MS the two-dimensional phenyl torsion potential energy surfaces and the one-dimensional carbon-carbon double bond torsional potential energy functions for both the S₀ and S₁((pi) , (pi) *) states were determined. The barriers to simultaneous phenyl internal rotation are 3100 cm^-1 for the ground state and 3000 cm^-1 for the excited state. The data for the C equals C torsion are consistent with a trans yields cis barrier of 48.3 kcal/mole for the S₀ state and a trans yields twist barrier of 2000 to 3500 cm^-1 for the S₁ state. For MS the barrier for simultaneous phenyl torsion for both the S₀ and S₁ states is 2860 cm^-1. The C equals C torsional barrier for MS in both the S₀ and S₁ states is approximately 10% higher than that of t-S.

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Jaan Laane, W.-Y. Chiang, K. Haller, and A. del Rosario "Jet-cooled fluorescence spectra, Raman spectra, and potential energy surfaces of stilbenes", Proc. SPIE 2548, Laser Techniques for State-Selected and State-to-State Chemistry III, (18 September 1995); https://doi.org/10.1117/12.220863

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KEYWORDS

Luminescence

Raman spectroscopy

Molecules

Argon ion lasers

Calibration

Liquids

Monochromators

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