Carsten L. Thomsen

TWO-PHOTON DISSOCIATION AND IONIZATION OF LIQUID WATER STUDIED BY FEMTOSECOND TRANSIENT ABSORPTION SPECTROSCOPY

The photodissociation and photoionization of liquid water following two-photon absorption at 266 nm is studied in the spectral range from 213 to 1108 nm with subpicosecond time resolution. Probing in the UV enables the first direct simultaneous observation of the photoproducts eaq−, Haq, and OHaq. This makes it possible to follow the geminate recombination kinetics between the photoproducts and to determine the relative yields of the dissociation and ionization channels. The concentration of hydrated electrons deduced from the visible and near-infrared transient absorption measurements decays by 40%±2% within the first 90 ps due to recombination with OHaq and H3O+. Analyzing our measurements of the hydrated electron concentration using the independent reaction time approximation results in the relative yields of 82%±3% and 18%±3% for recombination with OHaq and with H3O+, respectively. This is in excellent agreement with the relative yield of 82%±10% for recombination with OHaq determined directly from ou...

Supercontinuum generation in ZBLAN fibers—detailed comparison between measurement and simulation

We present a detailed comparison between modeling and experiments on supercontinuum (SC) generation in a commercial ZBLAN step-index fiber. Special emphasis is put on identifying accurate material parameters by incorporating measurements of the ZBLAN Raman gain, fiber dispersion, and loss. This identification of accurate parameters is of great importance to substantiate numerical simulations of SC generation in soft-glass fibers. Good agreement between measurement and simulation is obtained when pumping both in the normal and anomalous dispersion regimes.

Back-seeding of higher order gain processes in picosecond supercontinuum generation.

In photonic crystal fibers with closely spaced zero dispersion wavelengths it is possible to have two pairs of four-wave mixing (FWM) gain peaks. Here, we demonstrate both numerically and experimentally how the outer four-wave mixing gain peaks can be used to produce a strong amplification peak in a picosecond supercontinuum. The method involves feeding back part of the output light of a SC source and time matching it with the pump light. In this way it is possible to produce a gain of over 20 dB near the FWM gain wavelengths.

Influence of pump power and modulation instability gain spectrum on seeded supercontinuum and rogue wave generation

The noise properties of a supercontiuum can be significantly improved both in terms of coherence and intensity stability by modulating the input pulse with a seed. In this paper, we numerically investigate the influence of the seed wavelength, the pump power, and the modulation instability gain spectrum on the seeding process. The results can be clearly divided into a number of distinct dynamical regimes depending on the initial four-wave mixing process. We further demonstrate that seeding can be used to generate coherent and incoherent rogue waves, depending on the modulation instability gain spectrum. Finally, we show that the coherent pulse breakup afforded by seeding is washed out by turbulent solitonic dynamics when the pump power is increased to the kilowatt level. Thus our results show that seeding cannot improve the noise performance of a high power supercontinuum source.

Optimum fiber tapers for increasing the power in the blue edge of a supercontinuum-group-acceleration matching.

We demonstrate how the gradient of the tapering in a tapered fiber can significantly affect the trapping and blueshift of dispersive waves (DWs) by a soliton. By modeling the propagation of a fundamental 10 fs soliton through tapered fibers with varying gradients, it is shown that the soliton traps and blueshifts an increased fraction of the energy in its DW when the gradient is decreased. This is quantified by the group-acceleration mismatch between the soliton and DW at the entrance of the taper. These findings have direct implications for the achievable power in the blue edge of a supercontinuum generated in a tapered fiber and explain observations of a lack of power in the blue edge.

Power dependence of supercontinuum noise in uniform and tapered PCFs

We experimentally investigate the noise properties of picosecond supercontinuum spectra generated at different power levels in uniform and tapered photonic crystal fibers. We show that the noise at the spectral edges of the generated supercontinuum is at a constant level independent on the pump power in both tapered and uniform fibers. At high input power the spectral bandwidth is limited by the infrared loss edge, this however has no effect on the noise properties.

VIBRATIONAL RELAXATION OF CLO2 IN WATER

Photodissociation of ClO2 in aqueous solution at 400 nm results in the formation of ClO+O and Cl+O2. ClO and O geminately recombine to ClO2 in the electronic ground state (2B1), formed with an initial vibrational energy of ≈2.5 eV. In this paper the vibrational relaxation of ClO2(2B1) in aqueous solution is studied by femtosecond transient absorption spectroscopy in the spectral range 234 to 1024 nm. The measured transient absorption of the vibrationally relaxing ClO2 molecules is compared with the transient absorption calculated for relaxation in the asymmetric stretch as well as the symmetric stretch and bending modes. The calculations of the absorption spectra pertaining to the asymmetric stretch are based on a harmonic potential derived from the experimentally determined fundamental vibrational energy, whereas that of the symmetrical vibrations are based on ab initio potentials. An excellent agreement is obtained by assuming that the vibrational relaxation predominantly occurs in the asymmetric stretc...

Temperature dependent relaxation and recombination dynamics of the hydrated electron

The ultrafast solvation and recombination dynamics of the hydrated electron generated by two-photon ionization of water at 4.65 eV is studied by transient absorption spectroscopy as a function of temperature in the range from 277 K to 355 K. The part of the spectral blue shift which is observed in the absorption spectrum of the hydrated electron after 1 ps is purely continuous and is accurately described by the well known analytical expression for the temperature dependent absorption spectrum of the ground state hydrated electron. This indicates that thermal relaxation or more likely solvation of the hydrated electron predominantly causes the blue shift. The survival probability of the hydrated electron shows a strong temperature dependence, which is satisfactory explained by the temperature dependent mobility and reaction rates of the species involved in the recombination. This implies that the average initial separation between the hydrated electron and the ionization site of 〈r0〉=1.0±0.1 nm does not de...

Deep-blue supercontinnum sources with optimum taper profiles--verification of GAM.

We use an asymmetric 2 m draw-tower photonic crystal fiber taper to demonstrate that the taper profile needs careful optimisation if you want to develop a supercontinuum light source with as much power as possible in the blue edge of the spectrum. In particular we show, that for a given taper length, the downtapering should be as long as possible. We argue how this may be explained by the concept of group-acceleration mismatch (GAM) and we confirm the results using conventional symmetrical short tapers made on a taper station, which have varying downtapering lengths.

Femtosecond photolysis of aqueous HOCl

This paper reports an experimental study of the photolysis of aqueous HOCl using femtosecond pulses at 266 nm. The formation of photoproducts is monitored by transient absorption spectroscopy from 230 to 400 nm. The HOCl molecules dissociate with unity quantum yield to form OH+Cl faster than 1 ps, and as a result of the potential along the HO–Cl reaction coordinate, all excess energy is given to the fragments as translational energy. After dissociation, and solvent cage escape, the majority of the Cl and OH fragments recombine after diffusion on a time scale of 50 ps. The diffusion dynamics is studied using a simple model for diffusive recombination and a more extensive molecular dynamics simulation. A minor fraction of the Cl atoms (∼10%) reacts with HOCl in a diffusion limited reaction to form Cl2+OH.