Direct Observation of Coherent Oscillations in Solution due to Microheterogeneous Environment

We report, for the first time, direct observation of coherent oscillations in the ground-state of IR775 dye due to microheterogeneous environment. Using ultrafast near-infrared degenerate pump-probe technique centered at 800 nm, we present the dynamics of IR775 in a binary mixture of methanol and chloroform at ultra-short time resolution of 30 fs. The dynamics of the dye in binary mixtures, in a time-scale of a few fs to ~740 ps, strongly varies as a function of solvent composition (volume fraction). Multi-oscillation behavior of the coherent vibration was observed, which increased with decreasing percentage of methanol in the dye mixture. Maximum number of damped oscillations were observed in 20% methanol. The observed vibrational wavepacket motion in the ground-state is periodic in nature. We needed two cosine functions to fit the coherent oscillation data as two different solvents were used. Dynamics of the dye molecule in binary mixtures can be explained by wavepacket motion in the ground potential energy surface. More is the confinement of the dye molecule in binary mixtures, more is the number of damped oscillations. The vibrational cooling time, τ₂, increases with increase in the confinement of the system. The observed wavepacket oscillations in ground-state dynamics continued until 1.6 ps.