Ultrafast Solvation Dynamics of an Ion in the gamma-Cyclodextrin Cavity: The Role of Restricted Environment

A detailed study of the solvation dynamics of a charged coumarin dye molecule in gamma-cyclodextrin/water has been carried out by using two different theoretical approaches. The first approach is based on a multishell continuum model (MSCM). This model predicts the time scales of the dynamics rather well, provided an accurate description of the frequency-dependent dielectric function is supplied. The reason for this rather surprising agreement is 2-fold. First, there is a cancellation of errors, second, the two-zone model mimics the heterogeneous microenvironment surrounding the ion rather well. The second approach is based on the molecular hydrodynamics theory (MI-IT). In this molecular approach, the solvation dynamics has been studied by restricting the translational motion of the solvent molecules enclosed within the cavity. The results from the molecular theory are also in good agreement with the experimental results. Our study indicates that, in the present case, the restricted environment affects only the long time decay of the solvation time correlation function. The short time dynamics is still governed by the librational (and/or vibrational) modes present in bulk water.

Ultrafast Raman loss spectroscopy

This paper deals with a new form of nonlinear Raman spectroscopy called `ultrafast Raman loss spectroscopy (URLS)'. URLS is analogous to stimulated Raman spectroscopy (SRS) but is much more sensitive than SRS. The signals are background (noise) free unlike in coherent anti-Stokes Raman spectroscopy (CARS) and it provides natural fluorescence rejection, which is a major problem in Raman spectroscopy. In addition, being a self-phase matching process, the URLS experiment is much easier than CARS, which requires specific phase matching of the laser pulses. URLS is expected to be alternative if not competitive to CARS microscopy, which has become a popular technique in applications to materials, biology and medicine.

Analytical studies of gain optimization in CO2-N2 gasdynamic lasers employing two-dimensional wedge nozzles

An analytical method has been proposed to optimise the small-signaloptical gain of CO2-N2 gasdynamic lasers (gdl) employing two-dimensional (2D) wedge nozzles. Following our earlier work the equations governing the steady, inviscid, quasi-one-dimensional flow in the wedge nozzle of thegdl are reduced to a universal form so that their solutions depend on a single unifying parameter. These equations are solved numerically to obtain similar solutions for the various flow quantities, which variables are subsequently used to optimize the small-signal-gain. The corresponding optimum values like reservoir pressure and temperature and 2D nozzle area ratio also have been predicted and graphed for a wide range of laser gas compositions, with either H2O or He as the catalyst. A large number of graphs are presented which may be used to obtain the optimum values of small signal gain for a wide range of laser compositions without further computations.

Ultrafast and reversible multiblock formation by the SET-Nitroxide radical coupling reaction

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50◦C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br)with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

Ultrafast Raman loss spectroscopy: a new approach to vibrational structure determination

The rapid data acquisition, natural fluorescence rejection and experimental ease are the advantages of the ultra-fast Raman loss scattering (URLS) which makes it a unique and valuable molecular structure-determining technique. URLS is an analogue of stimulated Raman scattering (SRS) but far more sensitive than SRS. It involves the interaction of two laser sources, viz. a picosecond (ps) pulse and white light, with the sample leading to the generation of loss signal on the higher energy (blue) side with respect to the wavelength of the ps pulse, unlike the gain signal observed on the red side in SRS. These loss signals are at least 1.5 times more intense than the SRS signals. Also, the very prerequisite of the experimental protocol for signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which always appears on the red side. Unlike coherent anti-Stokes Raman scattering, URLS signals are not precluded by non-resonant background under resonance condition and also being a self-phase matched process, it is experimentally easier.

Stability criteria for single pulse solutions of cw passive mode-locked lasers

The stability of the steady-state solutions of mode-locking of cw lasers by a fast saturable absorber is imvestigated. It is shown that the solutions are stable if the condition (Ps/Pa) = (2/3) (P0Pa) is satisfied, where (Ps/Pa) is the steady-state la ser power, (P0/Pa) is the power at mode-locking threshold, and Pa is the saturated power of the absorber.

Theoretical gain optimization studies in CO2-N2 lasers. III. Inclusion of line shape effects

The influence of Lorentz and Doppler line-broadening mechanisms on the small-signal optical gain of lasers and, in particular, gasdynamic lasers, is discussed. A relationship between the critical parameter reflecting the line-broadening mechanisms and some of the important parameters arising out of the gain optimization studies in CO2-N2 gasdynamic lasers is established. Using this relationship, methods by which the deleterious effect of the Doppler mechanisms on small-signal gain can be suppressed are suggested. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Ultrafast Switching Time and Third Order Nonlinear Coefficients of Microwave Treated Single Walled Carbon Nanotube Suspensions

Microwave treated water soluble and amide functionalized single walled carbon nanotubes have been investigated using femtosecond degenerate pump-probe and nonlinear transmission experiments. The time resolved differential transmission using 75 femtosecond pulse with the central wavelength of 790 nm shows a bi-exponential ultrafast photo-bleaching with time constants of 160 fs (130 fs) and 920 fs (300 fs) for water soluble (amide functionalized) nanotubes. Open and closed aperture z-scans show saturation absorption and positive (negative) nonlinear refraction for water soluble (amide functionalized) nanotubes. Two photon absorption coefficient, beta(0) similar to 250 cm/GW (650 cm/GW) and nonlinear index, gamma similar to 15 cm(2)/pW (-30 cm(2)/pW) are obtained from the theoretical fit in the saturation limit to the data for two types of nanotubes.

Double walled carbon nanotubes as ultrafast optical switches

Pristine and molybdenum filled double walled carbon nanotubes (DWNTs) suspended in D2O show excellent ultrafast optical switching properties investigated through femtosecond Z-scan and degenerate pump-probe method using 50 fs pulses with central photon energy of 1.57 eV. For pristine-DWNT, the two photon absorption coefficient, beta and nonlinear refraction coefficient, n2 are 4.9×10−8 cm/W, and 9.5×10−11 cm2/W, respectively, which yield one photon figure of merit, W=133 and two photon figure of merit, T=0.4. The degenerate pump-probe measurements show strong photoinduced bleaching with biexponential decay with time constants ~150 and 600 fs. ©2009 American Institute of Physics

Theoretical gain optimization studies in 10.6 µm CO2-N2 gasdynamic lasers. IV. Further results of parametric study

Based on a method proposed by Reddy and Shanmugasundaram, similar solutions have been obtained for the steady inviscid quasi-one-dimensional nonreacting flow in the supersonic nozzle of CO2-N2-H2O and CO2-N2-He gasdynamic laser systems. Instead of using the correlations of a nonsimilar function NS for pure N2 gas, as is done in previous publications, the NS correlations are computed here for the actual gas mixtures used in the gasdynamic lasers. Optimum small-signal optical gain and the corresponding optimum values of the operating parameters like reservoir pressure and temperature and nozzle area ratio are computed using these correlations. The present results are compared with the previous results and the main differences are discussed. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Theoretical gain optimization in CO2-N2-H2 gasdynamic lasers with two-dimensional wedge nozzles

Attention is given to the results of optimization studies with a 16-micron CO2-N2-H2 GDL employing two-dimensional wedge nozzles. The optimum value of the achievable gain reaches 12.7 percent/cm on the P(15) line for a 30:50:20 percent respective apportionment of the aforementioned gases. The corresponding optimum values for reservoir pressure and area ratio are computed as functions of reservoir temperature, and presented graphically.

Dynamics of free-running, pump-modulated and coupled semiconductor and solid-state lasers

The output of a laser is a high frequency propagating electromagnetic field with superior coherence and brightness compared to that emitted by thermal sources. A multitude of different types of lasers exist, which also translates into large differences in the properties of their output. Moreover, the characteristics of the electromagnetic field emitted by a laser can be influenced from the outside, e.g., by injecting an external optical field or by optical feedback. In the case of free-running solitary class-B lasers, such as semiconductor and Nd:YVO4 solid-state lasers, the phase space is two-dimensional, the dynamical variables being the population inversion and the amplitude of the electromagnetic field. The two-dimensional structure of the phase space means that no complex dynamics can be found. If a class-B laser is perturbed from its steady state, then the steady state is restored after a short transient. However, as discussed in part (i) of this Thesis, the static properties of class-B lasers, as well as their artificially or noise induced dynamics around the steady state, can be experimentally studied in order to gain insight on laser behaviour, and to determine model parameters that are not known ab initio. In this Thesis particular attention is given to the linewidth enhancement factor, which describes the coupling between the gain and the refractive index in the active material. A highly desirable attribute of an oscillator is stability, both in frequency and amplitude. Nowadays, however, instabilities in coupled lasers have become an active area of research motivated not only by the interesting complex nonlinear dynamics but also by potential applications. In part (ii) of this Thesis the complex dynamics of unidirectionally coupled, i.e., optically injected, class-B lasers is investigated. An injected optical field increases the dimensionality of the phase space to three by turning the phase of the electromagnetic field into an important variable. This has a radical effect on laser behaviour, since very complex dynamics, including chaos, can be found in a nonlinear system with three degrees of freedom. The output of the injected laser can be controlled in experiments by varying the injection rate and the frequency of the injected light. In this Thesis the dynamics of unidirectionally coupled semiconductor and Nd:YVO4 solid-state lasers is studied numerically and experimentally.