Mahesh Namboodiri

Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) is used as a probe for monitoring the vibrational dynamics of room temperature ionic liquids (ILs). The experiments are performed on a series of 1,3-dialkylimidazolium ILs containing the bis(trifluoromethylsulfonyl)imide [NTf2] anion. The effect of methylation of the cationic C2 position on the dephasing time is studied analyzing [NTf2]-ILs of 1-ethyl-3-methylimidazolium [EMIM], 1-ethyl-2,3-dimethylimidazolium [EMMIM], 1-butyl-3-methylimidazolium [BMIM], and 1-butyl-2,3-dimethylimidazolium [BMMIM]. Raman coherences are excited around ∼1400 cm(-1), and the vibrational dephasing of the modes in the fingerprint region is monitored as a function of time. The results indicate that vibrational energy transfer occurs governed by the interionic interactions. This is suggested by mode beating involving vibrations beyond the excitation spectrum as well as systematic differences in the temporal dephasing behavior. In contrast, the length of the cationic alkyl side chain has a negligible impact on the vibrational dynamics.

Pump-probe scanning near field optical microscopy: Sub-wavelength resolution chemical imaging and ultrafast local dynamics

Results of two color femtosecond time-resolved pump-probe experiments using scanning near field optical microscopy on thin films of organic semiconductor 3,4,9,10 perylenetetracarboxylic dianhydride are presented. With this technique, quantitative information on exciton dynamics with high temporal and spatial resolution can be obtained by fitting a rate model to the transient absorption spectra. Additionally, the chemical selectivity inherent to this technique enhances the contrast, which could be used for video-rate imaging when high-repetition rate lasers are used.

Investigation of molecular dynamics in β-carotene using femtosecond pump-FWM spectroscopy

We have carried out two different pump four-wave mixing experiments, combining an initial pump excitation and a subsequent four-wave mixing probe process, on the photosynthetic pigment β-carotene to reveal different aspects of its molecular dynamics after photoexcitation. Firstly, the pump degenerate four-wave mixing (pump -DFWM) technique, in which the DFWM is resonant with the S1- to Sn-transition of β-carotene, is used to monitor the events following excitation of the system. The transient shows a peculiar shape and is seen to depend on the energy of the initial pump pulse as well as on the concentration of the solute in the solvent. Secondly, pump coherent anti-Stokes Raman scattering (pump-CARS) is used to elucidate the excited state vibrational dynamics of β-carotene. This technique gives access to the dynamics of both ground and excited electronic states with vibrational selectivity.

Two-photon resonances in femtosecond time-resolved four-wave mixing spectroscopy: β-carotene

Femtosecond time-resolved pump-degenerate four-wave mixing (pump-DFWM) spectroscopy has been used to study the ultrafast dynamics of beta-carotene involving several electronic and vibrational states. An initial pump pulse, resonant with the S(0)-to-S(2) transition, excites the molecular system and a DFWM process, resonant with the S(1)-to-S(n) transition, is used to probe the relaxation pathways. The transient shows a peculiar decay behavior, which is due to the contributions of resonant DFWM signal of the excited S(1) state, nonresonant DFWM signal of the ground S(0) state and vibrational hot S(0)* state, and the two-photon resonant DFWM signal of the ground S(0) state. We have used a kinetic model including all the signal contributions to successfully fit the transient. The time constants extracted are in very good agreement with the known values for beta-carotene. For comparison, a two-pulse pump-probe experiment was performed measuring the transient absorption at the wavelength of the DFWM experiment.

Nonlinear spectroscopy in the near-field: time resolved spectroscopy and subwavelength resolution non-invasive imaging

Abstract The combination of near-field microscopy along with nonlinear optical spectroscopic techniques is presented here. The scanning near-field imaging technique can be integrated with nonlinear spectroscopic techniques to improve spatial and axial resolution of the images. Additionally, ultrafast dynamics can be probed down to nano-scale dimension. The review shows some examples for this combination, which resulted in an exciton map and vibrational contrast images with sub-wavelength resolution. Results of two-color femtosecond time-resolved pump-probe experiments using scanning near-field optical microscopy (SNOM) on thin films of the organic semiconductor 3,4,9,10 Perylenetetracarboxylic dianhydride (PTCDA) are presented. While nonlinear Raman techniques have been used to obtain highly resolved images in combination with near-field microscopy, the use of femtosecond laser pulses in electronic resonance still constitutes a big challenge. Here, we present our first results on coherent anti-Stokes Raman scattering (fs-CARS) with femtosecond laser pulses detected in the near-field using SNOM. We demonstrate that highly spatially resolved images can be obtained from poly(3-hexylthiophene) (P3HT) nano-structures where the fs-CARS process was in resonance with the P3HT absorption and with characteristic P3HT vibrational modes without destruction of the samples. Sub-diffraction limited lateral resolution is achieved. Especially the height resolution clearly surpasses that obtained with standard microCARS. These results will be the basis for future investigations of mode-selective dynamics in the near-field.

Selective Probing of Vibrational Hot States in Bromine Using Time-Resolved Coherent Anti-Stokes Raman Scattering

In previous work (Scaria, A.; et al. Chem. Phys. Lett. 2009, 470, 39-43) it was shown that the excitation of the electronic B state in bromine can be characterized by transitions starting from vibrational hot states of the electronic ground X state. This contribution is strongly depending on the specific Franck-Condon factors for the chosen wavelength (in that work 540 nm) used for excitation. For the investigation of the resulting excited state dynamics, a pump-degenerate four-wave mixing (pump-DFWM) experiment was applied. To increase the vibrational selectivity, in the present work we have performed temperature-dependent time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy to probe the B state dynamics of bromine. Also here, the wavelength of the excitation (in this case, the pump laser of the CARS process) was set to 540 nm for all measurements. The hot state contribution is small, even at high temperatures. It can be probed by tuning the Stokes wavelength to resonance. The time delay between the probe pulse and the time-coincident pump/Stokes pulse pair of the CARS process is scanned, giving access to the wave packet dynamics in the excited B state. The experimental observations are supported by quantum dynamical calculations.

Scanning near-field optical coherent anti-Stokes Raman microscopy (SNOM-CARS) with femtosecond laser pulses in vibrational and electronic resonance

Accessing ultrafast photoinduced molecular dynamics on a femtosecond time-scale with vibrational selectivity and at the same time sub-diffraction limited spatial resolution would help to gain important information about ultrafast processes in nanostructures. While nonlinear Raman techniques have been used to obtain highly resolved images in combination with near-field microscopy, the use of femtosecond laser pulses in electronic resonance still constitutes a big challenge. Here, we present our first results on coherent anti-Stokes Raman scattering (fs-CARS) with femtosecond laser pulses detected in the near-field using scanning near-field optical microscopy (SNOM). We demonstrate that highly spatially resolved images can be obtained from poly(3-hexylthiophene) (P3HT) nano-structures where the fs-CARS process was in resonance with the P3HT absorption and with characteristic P3HT vibrational modes without destruction of the samples. Sub-diffraction limited lateral resolution is achieved. Especially the height resolution clearly surpasses that obtained with standard microCARS. These results will be the basis for future investigations of mode-selective dynamics in the near field.

Nonlinear Raman Techniques in Femtosecond Time Resolved Spectroscopy for the Analysis and Control of Molecular Dynamics

The use of four‐wave mixing techniques in femtosecond time‐resolved spectroscopy has considerable advantages. Due to the many degrees of freedom offered e.g. by coherent anti‐Stokes Raman scattering (CARS), the dynamics even of complex systems can be analyzed in detail. Using pulse shaping techniques in combination with a self‐learning loop approach, molecular mode excitation can be controlled very efficiently in a multi‐photon excitation process. Results obtained from the optimal control of CARS on β‐carotene are discussed.

Realization of an ultrafast all-optical Toffoli logic gate based on the phase relation between two second order nonlinear optical signals

A Toffoli logic gate (CCNOT gate) is a universal reversible logic gate from which all other reversible gates can be constructed. It has a three-bit input and output. The goal of our work was to realize a Toffoli gate where all inputs and outputs are realized optically, which allows for ultrafast switching processes. We demonstrate experimentally that a Toffoli logic gate can be created based on nonlinear multi-wave interactions of light with matter. Using femtosecond laser pulses, the all-optical Toffoli gate is based on the coherence of the optical signals produced via the nonlinear optical processes. Sum frequency (SF) and second harmonic (SH) generations are combined in such a way so as to yield the complete truth table of the universal reversible logic gate.

Transient Grating Studies of Femtosecond Processes in Ultra‐Thin Layers of PTCDA

Elementary processes like energy transfer, charge transport, and exciton diffusion in thin films occur on time scales of femtoseconds. Time-resolved photo-electron spectroscopy, a technique limited to ultra-high vacuum environment and the proper choice of a substrate, has been used to study ultrafast processes in sub-nanometer thin films so far. Herein we show that a transient (population) grating created by the interference of laser pulses can be used to study ultrafast processes in such films under ambient conditions. Our investigations of exciton dynamics in 1.4±0.2 nm and 0.4±0.2 nm thin films, formed by nanocrystals of 3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA) on glass and mica, show that the dynamics differ with the crystal size, possibly due to the confinement induced changes in the electronic structure. The technique is sensitive enough to investigate the dynamics in systems, where only 20 % of the surface is covered by nano-crystals. We expect such an optical technique that is sensitive enough to study dynamics in few to sub-nanometer thin layers under ambient conditions to become important in investigating ultrafast dynamics on surfaces, interfaces, functionalized materials, organic semiconductors, and quantum phenomena in ordered structures of reduced dimensions, such as quantum dots and graphene sheets.