The molecular structural and Raman spectroscopic characteristics of fl-carotene and lycopene are investigated by density functional calculations. The effects of molecular structure and solvent environment on the Raman spectra are analyzed by comparing the calculated and measured results. It is found that the B3LYP/6-31G（d） method can predict the reasonable result for β-carotene, but the vl Raman activities of lycopene overflow at all the used theo- retical methods because of the longer conjugation length in β-carotene impedes the delocalization of ~r-electrons The calculated results indicate that the rotation of β-rings shortens the effective conjugation length, and results in higher frequency and lower activity of the vl mode in /q-carotene than lycopene. The measured vl bands of β-carotene and lycopene shift respectively to higher and lower frequencies in solution compared with that in crystals since the crystal packing forces can lead to different conformational variations in the carotenoids molecules. The polarized continuum model theoretical analysis suggests that solvent has slight （significant） effects on the Raman frequencies （intensities） of both carotenoids.
Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.
