Johanan H. Odhner

Triangular gold nanoplate growth by oriented attachment of Au seeds generated by strong field laser reduction.

The synthesis of surfactant-free Au nanoplates is desirable for the development of biocompatible therapeutics/diagnostics. Rapid Δ-function energy deposition by irradiation of aqueous KAuCl4 solution with a 5 s burst of intense shaped laser pulses, followed by slow addition of H2O2, results in selective formation of nanoplates with no additional reagents. The primary mechanism of nanoplate formation is found to be oriented attachment of the spherical seeds, which self-recrystallize to form crystalline Au nanoplates.

Effect of two-beam coupling in strong-field optical pump-probe experiments

Nonlinear optics experiments measuring phase shifts induced in a weak probe pulse by a strong pump pulse must account for coherent effects that only occur when the pump and probe pulses are temporally overlapped. It is well known that a weak probe beam experiences a greater phase shift from a strong pump beam than the pump beam induces on itself. The physical mechanism behind the enhanced phase shift is diffraction of pump light into the probe direction by a nonlinear refractive index grating produced by interference between the two beams. For an instantaneous third-order response, the effect of the grating is to simply double the probe phase shift, but when delayed nonlinearities are considered, the effect is more complex. A comprehensive treatment is given for both degenerate and nondegenerate pump-probe experiments in noble and diatomic gases. Results of numerical calculations are compared to a recent transient birefringence measurement [Loriot et al., Opt. Express 17, 13429 (2009)] and a recent spectral interferometry experiment [Wahlstrand et al., Phys. Rev. A85, 043820 (2012)]. We also present results from two new experiments using spectrally resolved transient birefringence with 800 nm pulses in Ar and air and degenerate chirped pulse spectral interferometry in Ar. Both experiments support the interpretation of the negative birefringence at high intensity as arising from a plasma grating.

Direct phase and amplitude characterization of femtosecond laser pulses undergoing filamentation in air

Measurement of the temporal (spectral) phase and amplitude of a 50 fs laser pulse approaching and exceeding the critical power for self-focusing (P(crit)) in air reveals the formation of an isolated 17 fs pulse at 3P(crit). The dynamics of self-shortening are measured directly in the filament using transient-grating cross-correlation frequency-resolved optical gating with a noble gas serving as the nonlinear medium. Our results support recent filamentary propagation simulations, suggesting that a Kerr-dominated temporal reshaping process toward the end of the filament is largely responsible for the generation of short pulses.

Filament-driven impulsive Raman spectroscopy.

Vibrational Raman spectroscopy is performed in the gas phase using a femtosecond laser pulse undergoing filamentation as an impulsive excitation source. The molecular coherence induced by the filamentary pulse is subsequently probed using a narrowband, sub-picosecond laser pulse to produce Raman spectra of gas phase species in a few tens of milliseconds (~10 laser shots). Pulse shortening with concomitant spectral broadening during filamentation results in a pulse that is both sufficiently short and of sufficient spectral power density to impulsively excite the highest energy ground state vibrations (up to 4158 cm(-1) corresponding to H(2)). Gas phase detection of chloroform, methylene chloride, cyclohexane, toluene, pentane, triethylamine, ammonia, nitromethane, and gasoline is performed.

Elucidating Strong Field Photochemical Reduction Mechanisms of Aqueous [AuCl4](-): Kinetics of Multiphoton Photolysis and Radical-Mediated Reduction.

Direct, multiphoton photolysis of aqueous metal complexes is found to play an important role in the formation of nanoparticles in solution by ultrafast laser irradiation. In situ absorption spectroscopy of aqueous [AuCl4](-) reveals two mechanisms of Au(0) nucleation: (1) direct multiphoton photolysis of [AuCl4](-) and (2) radical-mediated reduction of [AuCl4](-) upon multiphoton photolysis of water. Measurement of the reaction kinetics as a function of solution pH reveals zeroth-, first-, and second-order components. The radical-mediated process is found to be zeroth-order in [AuCl4](-) under acidic conditions, where the reaction rate is limited by the production of reactive radical species from water during each laser shot. Multiphoton photolysis is found to be first order in [AuCl4](-) at all pHs, whereas the autocatalytic reaction with H2O2, the photolytic reaction product of water, is second order.

Optical Spectroscopy Using Gas-Phase Femtosecond Laser Filamentation

Femtosecond laser filamentation occurs as a dynamic balance between the self-focusing and plasma defocusing of a laser pulse to produce ultrashort radiation as brief as a few optical cycles. This unique source has many properties that make it attractive as a nonlinear optical tool for spectroscopy, such as propagation at high intensities over extended distances, self-shortening, white-light generation, and the formation of an underdense plasma. The plasma channel that constitutes a single filament and whose position in space can be controlled by its input parameters can span meters-long distances, whereas multifilamentation of a laser beam can be sustained up to hundreds of meters in the atmosphere. In this review, we briefly summarize the current understanding and use of laser filaments for spectroscopic investigations of molecules. A theoretical framework of filamentation is presented, along with recent experimental evidence supporting the established understanding of filamentation. Investigations carried out on vibrational and rotational spectroscopy, filament-induced breakdown, fluorescence spectroscopy, and backward lasing are discussed.

Spectral-to-Temporal Amplitude Mapping Polarization Spectroscopy of Rotational Transients

A new implementation of pump-probe polarization spectroscopy is presented where the revivals of an impulsively excited rotational wavepacket are mapped onto a broad-band, chirped continuum pulse to measure a long temporal window without the need for delay scanning. Experimental measurements and a theoretical framework for spectral-temporal amplitude mapping polarization spectroscopy (STAMPS) as applied to impulsive rotational motion are presented. In this technique, a femtosecond laser pulse is used to prepare a rotational wavepacket in a gas-phase sample at room temperature. The rotational revivals of the wavepacket are then mapped onto a chirped continuum (400-800 nm) pulse created by laser filamentation in argon. Nearly single-shot time-resolved rotational spectra are recorded over a 65 ps time window. The transient birefringence spectra are simulated by including terms for polarization rotation of the probe as well as cross-phase modulation. Measurements and simulations are presented for the cylindrically symmetric N2, O2, and CO2 molecules. The long time window of the method allows measurement of rotational spectra for asymmetric top molecules, and here we present measurements for ethylene and methanol.

Gold Nanotriangle Formation through Strong-Field Laser Processing of Aqueous KAuCl4 and Postirradiation Reduction by Hydrogen Peroxide

Femtosecond laser irradiation of aqueous KAuCl4 followed by postirradiation reduction with hydrogen peroxide (H2O2) is investigated as a new approach for the synthesis of gold nanotriangles (AuNTs) without any added surfactant molecules. Laser irradiation was applied for times ranging from 5 to 240 s, and postirradiation reduction of the solutions was monitored by UV-vis spectroscopy. Laser processing of aqueous KAuCl4 for 240 s, where the full reduction of Au(III) occurred during irradiation, produced spherical gold nanoparticles (AuNPs) with an average size of 11.4 ± 3.4 nm. Irradiation for shorter times (i.e., 15 s) resulted in the formation of laser-generated AuNP seeds (5.7 ± 1.8 nm) in equilibrium with unreacted KAuCl4 after termination of laser irradiation. The postirradiation reduction of these solutions by H2O2 produced a mixture of spherical and triangular AuNPs. Decreasing the laser irradiation time from 45 to 5 s significantly reduced the number of laser-generated Au seeds, the amount of H2O2 produced, and the rate of postirradiation reduction, resulting in the formation of a large number of AuNTs with sizes increasing from 29.5 ± 10.2 to 125 ± 43.2 nm. Postirradiation reduction is kinetically inhibited in the absence of laser-generated AuNP seeds.

Resolving the source of blue luminescence from alkyl-capped silicon nanoparticles synthesized by laser pulse ablation

Photoluminescence from alkyl-capped silicon nanoparticles (Si NPs) synthesized by laser ablation of silicon in 1-octene is found to originate from two distinct species: narrowband UV-emitting alkyl-capped Si NPs and broadly tuneable (350–500 nm) emission associated with a solvent by-product. Our results demonstrate the need to effectively separate solvent by-products, a step which is often overlooked in ablation studies, before characterizing the optical properties of ablation-synthesized NPs for luminescence applications.

Filament-Assisted Impulsive Raman Spectroscopy of Ozone and Nitrogen Oxides.

The filament-assisted impulsive Raman spectra of ozone, nitric oxide, and nitrogen dioxide are presented. The Raman response as a function of ozone concentration scales as N(2), where N is the number of oscillators in the interaction region. The system described has a detection limit of ∼300 ppm for gas-phase ozone. Ozone produced via the strong field chemistry occurring within the filament pump was also detected. The measurements reveal spectral interference in the Raman features. Simulations show the spectral fringing results from interference of the Raman signal with pump-induced cross-phase modulation. The fringes are used to classify the symmetric mode of the low concentration filament-generated ozone.