The structural deformation of NO2 group induced by an intense femtosecond laser field of liquid nitromethane（NM）molecule is detected by time-and frequency-resolved coherent anti-Stokes Raman spectroscopy（CARS） technique with the intense pump laser. Here, we present the mechanism of molecular alignment and deformation. The CARS spectra and its FFT spectra of liquid NM show that the NO2 torsional mode couples with the CN symmetric stretching mode and that the NO2 group undergoes ultrafast structural deformation with a relaxation time of 195 fs. The frequency of the NO2 torsional mode in liquid NM（50.8±0.3 cm^-1） at room temperature is found. Our results prove the structural deformation of two groups in liquid NM molecule occur simultaneously in the intense laser field.
The structural deformation induced by intense laser field of liquid nitrobenzene（NB） molecule,a typical molecule with restricting internal rotation,is tracked by time- and frequency-resolved coherent anti-Stokes.Raman spectroscopy（CARS） technique with an intense pump laser.The CARS spectra of liquid NB show that the NO2 torsional mode couples with the NO2 symmetric stretching mode,and the NB molecule undergoes ultrafast structural deformation with a relaxation time of 265 fs.The frequency of NO2 torsional mode in liquid NB（42 cm-1） at room temperature is found from the sum and difference combination bands involving the NO2 symmetric stretching mode and torsional mode in time- and frequency-resolved CARS spectra.
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.
