Separating Ultrafast Ground and Excited State Vibrations

Abstract

Using „spectrally dispersed’ impulsive stimulated Raman spectroscopy, vibrational spectra arising from motion of nuclear wavepackets in ground and excited electronic states of iodine in carbon tetrachloride are recorded isolating from solvent modes.

A Revisit on Impulsive Stimulated Raman Spectroscopy: Importance of Spectral Dispersion of Chirped Broadband Probe

“…Impulsive pump–probe studies in the gas phase on diatomic molecules including halogens, in particular on iodine, led to the observation of wavepacket motion on repulsive/bound/quasicontinuum states and were explored in depth by using femtosecond transition-state spectroscopy. ,,, Therefore, it is intriguing to implement broadband ISRS to revisit the studies on iodine in condensed phase , to unravel specific solute–solvent contributions. In the following, a discussion on iodine in carbon tetrachloride at 620 nm is presented extending preliminary results communicated elsewhere …”

“…In the following, a discussion on iodine in carbon tetrachloride at 620 nm is presented extending preliminary results communicated elsewhere. 71 Depending upon the pump wavelength, the excited state can be prepared on a repulsive potential energy surface or on a bound potential energy surface or in the continuum. At 620 nm (partially resonant) pumping, the excited state in iodine is prepared around ν = 3 in the bound state (B), in addition to creation of vibrational wavepacket in the ground electronic state (X).…”