Calculations of absorption and emission spectra: A study of cis-stilbene
- 15 December 1992
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 97 (12), 8915-8925
- https://doi.org/10.1063/1.463366
Abstract
Absorption and emission spectra are calculated by modeling cis‐stilbene as a system of 12 displaced harmonic oscillators. We are able to obtain good agreement with the peaks of both the room temperature absorption and low temperature emission spectra using parameters from resonance Raman experiments by adjusting the position of the zero–zero transition energy (E0,0) and slightly adjusting the displacements along the normal modes. The best fit value for E0,0 is 29 000 cm−1. Using the displacements along the 12 degrees of freedom, and a normal mode description based on semiempirical quantum force field calculations (QCFF/PI), we determine a ‘‘relaxed’’ excited state geometry which is twisted a maximum of approximately 37 deg along the ethylenic torsional coordinate relative to the relaxed ground state geometry. An extension of the spectral calculations is described which allows for one or more of the modes to be anharmonic and vibrationally unrelaxed. We apply this extension to show that cis‐stilbene emission can not be originating from a geometry with a 90 deg twist along the ethylenic coordinate. Comparison of our results with a recently obtained room temperature solution phase emission spectrum suggest that this emission originates from vibrationally unrelaxed molecules.Keywords
This publication has 41 references indexed in Scilit:
- Femtosecond laser studies of the cis-stilbene photoisomerization reactions: the cis-stilbene to dihydrophenanthrene reactionThe Journal of Physical Chemistry, 1991
- Isomerization of cis-stilbene in rare-gas clusters: direct measurements of trans-stilbene formation rates on a picosecond time scaleJournal of the Optical Society of America B, 1990
- cis-Stilbene fluorescence in solution. Adiabatic 1c*.fwdarw.1t* conversionJournal of the American Chemical Society, 1990
- Intrinsic potential energy barrier for twisting in the trans-stilbene S1 state in hydrocarbon solventsThe Journal of Physical Chemistry, 1989
- The .DELTA.H for thermal trans/cis-stilbene isomerization: do S0 and T1 potential energy curves cross?The Journal of Physical Chemistry, 1987
- Interpretation of c i s-hexatriene absorption spectrum. The Duschinsky effectThe Journal of Chemical Physics, 1975
- Emissions of sterically hindered stilbene derivatives and related compounds. Part IV. Large conformational differences between ground and excited states of sterically hindered stilbenes: implications regarding stokes shifts and viscosity or temperature dependence of fluorescence yieldsJournal of the Chemical Society, Perkin Transactions 2, 1975
- Calculation of .pi..pi.* excited state conformations and vibronic structure of retinal and related moleculesJournal of the American Chemical Society, 1974
- Ultraviolet Spectra of Stilbene, p-Monohalogen Stilbenes, and Azobenzene and the trans to cis Photoisomerization ProcessThe Journal of Chemical Physics, 1962
- Kinetics of Thermal Cis-Trans Isomerization. IIIJournal of the American Chemical Society, 1934