Unusual cis-diprotonated forms and fluorescent aggregates of non-peripherally alkoxy-substituted metallophthalocyanines.

Protonation and aggregation of two metallophthalocyanines (zinc and magnesium) non-peripherally substituted with 1,4,7-trioxanonyl moieties were studied by steady-state and time-resolved optical spectroscopy. Both compounds are easily protonated in organic solvents, but the central metal ion strongly affects the character of this process. In particular, the magnesium derivative forms the cis-diprotonated isomer observed for the first time in phthalocyanines, in contrast to its zinc counterpart which forms the typical trans-diprotonated isomer. In addition, studies performed on phthalocyanines substituted with n-butoxy groups at their non-peripheral positions indicated that the formation of the cis-diprotonated forms is a more common feature of alkoxy-substituted magnesium metallophthalocyanines, in contrast to derivatives with other metal ions. The cis-diprotonated forms of the magnesium derivatives are formed at much lower proton concentrations than the trans-diprotonated forms of their zinc counterparts. The cis-isomers were also found to have more advantageous photophysical properties for photoactive applications than the trans-isomers. Aggregation studies of the trioxanonyl phthalocyanines revealed that the magnesium derivative aggregates much more easily in non-coordinating solvents than its zinc counterpart. Both the derivatives form fluorescent aggregates, which is typically attributed to the presence of oxygen-to-metal intermolecular coordination preventing the formation of non-fluorescent face-to-face stacks. The results indicate that the oxygen-to-metal coordination plays a significant role in the studied systems and the stronger oxygen-coordination ability of magnesium ions compared to zinc ions may underlie the observed differences between the phthalocyanines metallated with these two ions.

Passively modelocked, diode-pumped Yb:KYW femtosecond oscillator with 1 GHz repetition rate.

We demonstrate a high repetition rate, single mode fiber-coupled diode pumped, Yb:KYW laser in a four mirror ring cavity configuration and study its performance in soft aperture, Kerr lens mode-locked operation at around 1.04 microm.

Ground- and excited-state tautomerization rates in porphycenes.

The rates of double hydrogen transfer in the ground and excited electronic states have been measured for porphycene and its derivatives by using a new method based on pump-probe polarization spectroscopy. Changing the strength of two intramolecular hydrogen bonds by altering the NHN distance leads to differences in the tautomerization rate exceeding three orders of magnitude. The reaction is considerably slower in the lowest electronically excited state. A correlation was found between the tautomerization rates and (1)H chemical shifts of the internal protons.

Broadband noncollinear optical parametric amplifier using a single crystal.

A noncollinear optical parametric amplifier in which blue pump pulse generation as well as parametric amplification takes place in the same nonlinear crystal is presented. Broadband spectra tunable throughout over 100 nm in the visible were generated in a simple setup. The green output pulses were compressed to 65 fs, and efficiency (IR-to-visible) of 1.8% was achieved.

Femtosecond study of the interplay between excitons, trions, and carriers in (Cd,Mn)Te quantum wells.

We study the absorption by neutral excitons and positively charged excitons (trions) following a femtosecond, circularly polarized, resonant pump pulse. Three populations are involved: free holes, excitons, and trions, all exhibiting transient spin polarization. In particular, a polarization of the gas of free holes is created by the formation of trions. The evolution of these populations is described, including spin flip and trion formation. We evaluate the contributions of phase space filling and spin-dependent screening. We propose a new explanation of the oscillator strength stealing phenomena observed in doped quantum wells, based on the screening of neutral excitons by charge carriers. We have also found that binding holes into charged excitons excludes them from the interaction with the rest of the system, so that oscillator strength stealing is partially blocked.

Piezo-driven deformable mirror for femtosecond pulse shaping.

We have developed a deformable, gold-coated mirror based on piezoelectric actuators with 15-micros response time. With 20 independent channels we were able to compress 72-fs pulses from a Ti:sapphire oscillator down to 45 fs in a 4f zero-dispersion compressor arrangement. Spectral interference was used to measure the mirror performance, while the spectral phase interferometry for direct electric field reconstruction (SPIDER) technique was used for the laser pulse characterization.

Photography of shock waves during excimer laser ablation of the cornea. Effect of helium gas on propagation velocity.

Shadow photography of shock waves excited by means of a xenon chloride excimer laser was performed to determine the shock wave propagation velocity in air, nitrogen and helium. Energy densities between 500 and 2,000 mJ/cm2 were used to ablate a rotating rubber cylindrical target and porcine corneas. In ablating the rubber cylinder, a shock wave velocity of 3.3 km/s was generated in air and nitrogen at 40 ns; this decreased to 1.4 km/s at 320 ns. When helium was blown on the target, the velocity increased by a factor of approximately two, to 5.9 km/s at 40 ns and 2.7 km/s at 320 ns. We suggest that blowing helium on the surface of the cornea during excimer laser ablation may speed the dissipation of high-energy acoustic waves and gaseous particles, and thus reduce the exposure and transfer of heat energy to the surrounding tissue.

Increased efficiency for sum-frequency generation for broadband input fields.

A new method of efficient sum-frequency generation for broadband input fields is theoretically analyzed and experimentally demonstrated. The method involves using an arrangement with two or more nonlinear mixing crystals, with a time-delay line situated between the crystals, for one of the fundamental fields relative to the other. The delay line temporally shifts the fundamental fields, one relative to another, by a time longer than their coherence time. The improvement in efficiency for sum-frequency generation using this method is much higher than for difference-frequency generation.

Efficient high repetition rate synchronous amplification of a passively mode-locked femtosecond dye laser.

We demonstrate reliable operation of a stable synchronously pumped dye amplifier for femtosecond pulses from a passively mode-locked dye laser. Conversion efficiencies of 8% are obtained with output powers of 40 mW and 50-fs pulse widths at repetition rates of up to 10 kHz with pulse energy stability of 3% rms. Synchronization is achieved by driving the frequency-modulated mode-locked seed oscillator for the regenerative amplifier pump laser directly from the dye laser oscillator. Low timing jitter between the dye oscillator and seed laser of less than 1 ps leads to efficient amplification and low amplified spontaneous emission (1%) from the amplifier.

Phase cross correlation in the coherent Raman process.

The coherent anti-Stokes Raman scattering (CARS) process with two different-color phase-fluctuating fields was studied experimentally and theoretically. It was found that the efficiency of this process depends strongly on the cross correlation between the phases of the driving fields. Depending on the detuning from Raman resonance, the CARS signal can be either enhanced or suppressed with respect to the case of uncorrelated fields.

Temporal smoothing of multimode dye-laser pulses.

Pulses from a broadband dye laser operating in many modes have been temporally smoothed by passing them through a strongly saturated dye amplifier in the presence of a strong, nonsaturable absorber. The standard nonlinear coupled partial differential equations based on the rate-equation approximation have been used to model the amplifier. Both analytic and numerical solutions for the equations show that under attainable conditions the intensity of the amplified pulse follows the temporal shape of the pump pulse.