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.

Insights into the morphology of nanoclusters would facilitate the design of nano-devices with improved optical, electrical, and magnetic responses. We have utilized optical gradient forces for the directed self-assembly of colloidal clusters using high-repetition-rate femtosecond laser pulses to delineate their structure and dynamics. We have ratified our experiments with theoretical models derived from the Langevin equation and defined the valid ranges of applicability. Our femtosecond optical tweezer-based technique characterizes the in-situ formation of hierarchical self-assembled clusters of homomers as well as heteromers by analyzing the back focal plane displacement signal. This technique is able to efficiently distinguish between nano-particles in heterogeneous clusters and is in accordance with our theory. Herein, we report results from our technique, and also develop a model to describe the mechanism of such processes where corner frequency changes. We show how the corner frequency changes enables us to recognize the structure and dynamics of the coagulation of colloidal homogeneous and heterogeneous clusters in condensed media over a broad range of nanoparticle sizes. The methods described here are advantageous, as the backscatter position-sensitive detection probes the in-situ self-assembly process while other light scattering approaches are leveraged for the characterization of isolated clusters.

We illustrate control of a polarized laser optical trapping potential landscape through the nonideal mixing of binary liquids. The inherent trapping potential asymmetry (ITPA) present in the trapping region results from the asymmetric intensity distribution in focal volume due to the high numerical aperture objective lens. Experimentally, we show that this ITPA effect can be modified and/or removed by the use of binary liquid mixtures. From our femtosecond optical tweezers experiments, we determine the topograph of the trapping potential base on the fluctuation-dissipation theorem. Additionally, the Brownian motion of the trapped bead is sensitive to the frictional force (FF) of the surroundings that is exerted by clusters of water and alcohol binary mixture through extended hydrogen bonding. Thus, using these two effects, ITPA and FF of the medium, we have shown that one can indeed modify the effective trapping potential landscape. Water-alcohol binary mixtures display a nonlinear dependence on the microrheological properties of the solvent composition as a result of rigid cluster formation. Volumetrically, at about 30% methanol in water binary mixture, the trapping asymmetry is minimal. In this particular binary mixture composition, the hydrophobic part of the methanol molecule is surrounded by ‘cages’ of water molecules. Enhanced H-bonding network of water molecules results in higher viscosity, which contributes to the higher frictional force. Increased viscosity decreases the degree of anisotropy due to hindered dipolar rotation. However, at higher methanol concentrations, the methanol molecules are no longer contained within the water cages and are free to move, which decrease their overall bulk viscosity. Thus, for pure solvents, experimentally measured anisotropy matches quite well with the theoretical prediction, but this fails in case of the binary mixtures due to the increased frictional force exerted by binary mixtures that result from the formation of cage-like structures.

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