Jd. Leonard et Tl. Gustafson, THE 211 NM EXCITED RESONANCE RAMAN-SPECTRA OF TRANS-STILBENE AND RELATED MOLECULES, Journal of molecular structure, 379, 1996, pp. 109-120
We have obtained the 211 nm Raman spectra of trans-stilbene (tS), tran
s-stilbene oxide, triphenylethylene, and 4,4'-dimethoxystilbene. We co
mpare these spectra with the 211 nm Raman spectra of biphenyl (BP) and
1,4-diphenyl-1,3-butadiene (DPB). In an effort to elucidate the effec
t of solvent on the excited state potential energy surface, we calcula
te differential Raman cross-sections of the 1630 cm(-1) band of DPB an
d the 1610 cm(-1) band of BP at excitation wavelengths of 211 and 746
nm in acetonitrile, ethanol, and cyclohexane. The cross-sections for t
hese bands with 746 nm excitation increase with increasing solvent pol
arity in the order sigma(cyclohexane) < sigma(ethanol) < sigma(acetoni
trile). The trend is different with 211 nm excitation, sigma(acetonitr
ile) < sigma(cyclohexane) less than or equal to sigma(ethanol). We att
ribute the different trend at 211 nm S-0 microscopic interactions betw
een the solvent and the excited state of the solute molecules. We also
present a comparison of the 211 nm So resonance Raman spectra and the
S-1 resonance Raman spectra of tS and DPB.