This document is Sajad Azizi's doctoral thesis titled 'Three Aspects of Photoionization in Ultrashort Pulses.' The research was conducted under the supervision of Prof. Dr. Jan Michael Rost at the Max Planck Institute for the Physics of Complex Systems.:Contents 1 Introduction 1 1.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.2 Thesis outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2 Fundamental Concepts 5 2.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.2 Introduction to strong field ionization . . . . . . . . . . . . . . . . . . . . . . 6 2.2.1 From the photoelectric effect to strong-field ionization . . . . . . . . . 6 2.3 Non-relativistic time-dependent Hamiltonian . . . . . . . . . . . . . . . . . . 10 2.3.1 Dipole approximation and choice of gauges . . . . . . . . . . . . . . . 11 2.3.2 Interaction of an electron with a classical field . . . . . . . . . . . . . 12 2.4 Ultrashort laser pulse shaping . . . . . . . . . . . . . . . . . . . . . . . . . . 14 2.4.1 Fourier-limited pulse: Gaussian envelope . . . . . . . . . . . . . . . . . 17 2.4.2 Modulated pulse: sinusoidal phase modulation . . . . . . . . . . . . . 18 2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 3 Controlling Non-adiabatic Photoionization with Ultrashort Pulses 20 3.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3.2 Introduction to non-adiabatic ionization . . . . . . . . . . . . . . . . . . . . . 21 3.2.1 Intuitive picture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 3.2.2 Mathematical picture . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3.3 Non-adiabatic ionization with tailored laser pulses . . . . . . . . . . . . . . . 25 3.3.1 Ionization by single Gaussian pulses . . . . . . . . . . . . . . . . . . . 26 3.3.2 Sensitivity of non-adiabatic photoionization to the modulation phase . 28 3.3.3 The role of the catalyzing state . . . . . . . . . . . . . . . . . . . . . . 31 3.3.4 Second-order perturbation theory . . . . . . . . . . . . . . . . . . . . . 32 3.3.5 Pulse optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 4 Time-dependent Perturbation Theory for Ultrashort Pulses 37 4.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 4.2 Introduction to time-dependent perturbation theory . . . . . . . . . . . . . . 39 4.2.1 Higher order time-dependent perturbation theory . . . . . . . . . . . . 42 4.2.2 Perturbation theory in shaped short laser pulse . . . . . . . . . . . . . 45 4.3 Application I: non-adiabatic ionization . . . . . . . . . . . . . . . . . . . . . . 47 4.3.1 Slowly varying envelope approximation . . . . . . . . . . . . . . . . . 50 4.3.2 Zero-photon transition . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 4.3.3 Zero-photon ionization probability . . . . . . . . . . . . . . . . . . . . 55 4.3.4 Oscillation in zero-photon transition . . . . . . . . . . . . . . . . . . . 58 4.4 Application II: interference stabilization . . . . . . . . . . . . . . . . . . . . . 59 4.4.1 Third-order time-dependent perturbation theory . . . . . . . . . . . . 61 4.4.2 Ionization probability and stabilization . . . . . . . . . . . . . . . . . . 62 4.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 5 Molecular Photoionization Time Delay 65 5.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 5.2 Introduction to time delay . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 5.2.1 Time delay in scattering scenario . . . . . . . . . . . . . . . . . . . . 69 5.2.2 Asymptotic behavior of ⟨r⟩ . . . . . . . . . . . . . . . . . . . . . . . . 71 5.3 Photoionization time delay from a scattering theory perspective . . . . . . . 74 5.3.1 Asymptotic solutions and scattering matrix . . . . . . . . . . . . . . . 75 5.3.2 Energy normalization . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 5.3.3 Boundary condition and final molecular wavefunction . . . . . . . . . 79 5.3.4 Matrix element and photoionization time delay . . . . . . . . . . . . . 81 5.3.5 Two-center system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 5.4 Photoionization time delay from a wavepacket perspective . . . . . . . . . . 87 5.4.1 Partial time delay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 5.4.2 Photoelectron wavepacket and photoionization time delay . . . . . . . 92 5.4.3 Anisotropic potential and half-collision checking . . . . . . . . . . . . 94 5.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 6 Conclusions and Outlook 97 A Renormalized Numerov Method 101 A.1 Introduction to Numerov method . . . . . . . . . . . . . . . . . . . . . . . . 103 A.1.1 Eigenvalue calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 A.2 Johnson renormalized Numerov method . . . . . . . . . . . . . . . . . . . . . 106 A.2.1 Proper initialization for extreme values of potential . . . . . . . . . . . 108 A.2.2 Matching point and bound states solutions . . . . . . . . . . . . . . . 110 A.2.3 Discretized continuum states solutions . . . . . . . . . . . . . . . . . . 111 A.2.4 Continuum states solutions . . . . . . . . . . . . . . . . . . . . . . . . 112 B Derivation of the Asymptotic Behavior of ⟨r⟩ 114 C Classical Time Delay 117 D Temporal Airy Pulse 119 E Numerical Details of Perturbation Theory 122 F Atomic Units

The recent upsurge of multidrug resistant bacteria (MDRB) among global communities has become one of the most serious challenges facing health professionals and the human population worldwide. Cationic ultrashort antimicrobial peptides (USAMPs) are a promising group of molecules that meet the required criteria of novel antimicrobial drug development. UP-5, a novel penta-peptide, displayed significant antimicrobial activities against various standard and clinical isolates of MDRB. UP-5 displayed MICs values within the range of (10–15 M) and (55–65 M) against Gram-positive and Gram-negative bacteria, respectively. Furthermore, UP-5 displayed antibiofilm activity with minimum biofilm eradication concentration (MBEC) value as equal to twofold higher than MIC value. At the same inhibitory concentrations, UP-5 exhibited very low or negligible toxicity toward human erythrocytes and mammalian cells. Combining UP-5 with conventional antibiotics led to a synergistic or additive mode of action that resulted in the reduction of the MIC values for some of the antibiotics by 99.7% along a significant drop in MIC values of the peptide. The stability profile of UP-5 was evaluated in full mouse plasma and serum with results indicating a more stable pattern in plasma. The present study indicates that USAMPs are promising antimicrobial agents that can avoid the negative characteristics of conventional antimicrobial peptides. Additionally, USAMPs exhibit good to moderate activity against MDRB, negligible toxicity, and synergistic outcomes in combination with conventional antimicrobial agents.

In this thesis, advanced spectroscopy methods are discussed and applied to gain understanding of the physical properties of organic conjugated molecules, II-VI thin film semiconductors, and vertical cavity surface emitting lasers (VCSEL). Experiments include single photon and two-photon excitation with lasers, with subsequent measurements of the absorption and photoluminescence, as well as photocurrent measurements using tungsten and xenon lamps, measuring the direct current and the alternating current of the devices. The materials are investigated in dissolved form (conjugated polymers), thin films (polymers, II-VI semiconductors), and complex layer structures (hybrid device, VCSEL). The experiments are analyzed and interpreted by newly developed or applied theories for two-photon saturation processes in semiconductors, bandgap shrinkage due to optically induced electron hole pairs, and the principle of detailed balance to describe the photoluminescence in thin film cadmium sulfide. / Ph. D.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Low-dimensional materials are known to undergo phase transitions to differently or- dered states, when cooled to lower temperatures. These phases often show a periodic modulation of the charge density (called a charge density wave – CDW) coupled with a periodic perturbation of the crystal lattice (called a periodic lattice distortion – PLD). Although many experiments have been performed and much has been learnt about CDW phases in low-dimensional materials, the reasons for their existence are still not fully understood yet. Many processes, involving either strong electron–electron or electron–lattice coupling, have been observed which all might play a role in explaining the formation of different phases under different conditions. With the availability of femtosecond lasers it has become possible to study materials under highly nonequilibrium conditions. By suddenly introducing a known amount of energy into the system, the equilibrium state is disturbed and the subsequent relax- ation processes are then observed on timescales of structural and electronic responses. These experiments can deliver valuable information about the complex interactions between the different constituents of condensed matter, which would be inaccessible under equilibrium conditions. We use time resolved electron diffraction to investigate the behaviour of a CDW system perturbed by a short laser pulse. From the observed changes in the diffraction patterns we can directly deduce changes in the lattice structure of our sample. A femtosecond electron diffraction setup was developed at the Laser Research In- stitute in Stellenbosch, South Africa. Short laser pulses produce photo electrons which are accelerated to an energy of 30 keV. Despite space charge broadening effects, elec- tron pulses shorter than 500 fs at sample position can be achieved. Technical details of this system and its characterisation as well as sample preparation techniques and analysis methods are described in detail in this work. Measurements on two members of the quasi-two-dimensional transition metal di- chalcogenides, namely 4Hb-TaSe2 and 1T-TaS2, are shown and discussed. Both show fast (subpicosecond) changes due to the suppression of the PLD and a rapid heating of the lattice. When the induced temperature rise heats the sample above a phase tran- sition temperature, a complete transformation into the new phase was observed. For 4Hb-TaSe2 we found that the recovery to the original state is significantly slower if the PLD was completely suppressed compared to only disturbing it. On 1T-TaS2 we could not only study the suppression of the original phase but also the formation of the higher energetic CDW phase. Long (100 ps) time constants were found for the tran- sition between the two phases. These suggest the presence of an energy barrier which has to be overcome in order to change the CDW phase. Pinning of the CDW by de- fects in the crystal structure result in such an energy barrier and consequently lead to a phase of domain growth which is considerably slower than pure electron or lattice dynamics. / AFRIKAANSE OPSOMMING: Dit is bekend dat lae-dimensionele materie fase oorgange ondergaan na anders ge- ori¨enteerde toestande wanneer afgekoel word tot laer temperature. Hierdie fases toon dikwels ’n periodiese modulasie van die elektron digtheid (genoem ’n “charge density wave” – CDW), tesame met ’n periodiese effek op die kristalrooster (genoem ’n “peri- odic lattice distortion” – PLD). Alhoewel baie eksperimente al uitgevoer is en al baie geleer is oor hierdie CDW fase, is die redes vir hul bestaan nog steeds nie ten volle verstaan nie. Baie prosesse, wat of sterk elektron–elektron of elektron–fonon interaksie toon, is al waargeneem en kan ’n rol speel in die verduideliking van die vorming van die verskillende fases onder verskillende omstandighede. Met die beskikbaarheid van femtosekonde lasers is dit nou moontlik om materie onder hoogs nie-ewewig voorwaardes te bestudeer. Deur skielik ’n bekende hoeveel- heid energie in die stelsel in te voer, word die ewewigstaat versteur en word die daar- opvolgende ontspanning prosesse waargeneem op die tydskaal van atomies struktu- rele en elektroniese bewiging. Hierdie eksperimente kan waardevolle inligting lewer oor die komplekse interaksies tussen die verskillende atomiese komponente van ge- kondenseerde materie, wat ontoeganklik sou wees onder ewewig voorwaardes. Ons gebruik elektrondiffraksie met tyd resolusie van onder ’n pikosekonde om die gedrag van ’n CDW stelsel te ondersoek nadat dit versteur is deur ’n kort laser puls. Van die waargenome veranderinge in die diffraksie patrone kan ons direk aflei watse veranderinge die kristalstruktuur van ons monster ondergaan. ’n Femtosekonde elektronendiffraksie opstelling is ontwikkel by die Lasernavors- ingsinstituut in Stellenbosch, Suid-Afrika. Kort laser pulse produseer foto-elektrone wat dan na ’n energie van 30 keV versnel word. Ten spyte van Coulomb afstoting ef- fekte, kan elektron pulse korter as 500 fs by die monster posisie bereik word. Tegniese besonderhede van hierdie opstelling, tegnieke van die voorbereiding van monsters asook analise metodes word volledig in hierdie tesis beskryf. Metings op twee voorbeelde van kwasi-tweedimensionele semi-metale, naamlik 4Hb-TaSe2 en 1T-TaS2, word gewys en bespreek. Beide wys ’n vinnige (subpikosekon- de) verandering as gevolg van die versteuring van die PLD en ’n vinnige verhitting van die kristalrooster. Wanneer die ge¨ınduseerde temperatuur bo die fase oorgang tempe- ratuur styg, is ’n volledige transformasie na die nuwe fase waargeneem. Vir 4Hb-TaSe2 het ons gevind dat die herstelling na die oorspronklike toestand aansienlik stadiger is as die PLD heeltemal viernietig is in vergelyking met as die PLD net versteur is. Met 1T-TaS2 kon ons nie net alleenlik die vernietiging van die oorspronklike fase sien nie, maar ook die vorming van ’n ho¨er energie CDW fase. Lang (100 ps) tydkonstante is gevind vir die oorgang tussen die twee fases. Hierdie dui op die teenwoordigheid van ’n energie-versperring wat eers oorkom moet word om die CDW fase voledig te ver- ander. Vaspenning van die CDW deur defekte in die kristalstruktuur veroorsaak so’n energie versperring en gevolglik lei dit tot ’n fase van groeiende CDW gebiede wat heelwat stadiger as pure elektron of kritalrooster dinamika is.

This thesis reports on the development of glass-based femtosecond laser sources around 2 µm wavelength. In order to be able to produce 2 µm radiation the dopants used were trivalent Thulium (Tm³⁺) and trivalent Holmium (Ho³⁺) that could be optically pumped with Ti:Sapphire radiation at 0.8 µm and semiconductor disk lasers (SDL) at 1.2 µm. The samples were produced at Leeds University and polished in-house in bulk form and deployed in free space laser cavities. Tellurite compounds doped with Tm³⁺ produced stable continuous wave 1.94 µm radiation when pumped at 800 nm with a maximum efficiency of 28.4% with respect to the absorbed power and maximum output power around 120 mW when pumped using a Ti:Sapphire operating around 0.8 µm. The radiation was broadly tunable across 130 nm. Tm³⁺-Ho³⁺ doubly doped tellurite samples lased around 2.02 µm with maximum efficiency of 25.9% and with P[subscript(OUT)]=75 mW and a smooth tunability of 125 nm. The fluorogermanate glass doped with Tm³⁺ gave an absorbed to output power efficiency of 50%. The maximum continuous wave output powers obtained were around 190 mW and limited by the available pump power at 0.8 µm. These results together with a very low threshold of 60 mW of incident power were comparable to the crystalline counterparts to this gain medium. The Tm3+ tellurite and the Tm³⁺-Ho³⁺ tellurite compounds were also pumped by an SDL operating at 1215 nm to obtain an indication of the viability of such a pump scheme. The results were a maximum internal slope efficiency of 22.4% with a highest output power of 60 mW. The comparison demonstrated that 1.2 µm pumping was competitive with using 0.8 µm wavelength. The use of semiconductor saturable absorbing mirror (SESAM) technology was used for the modelocking of these lasers. The SESAM was produced in Canada and implanted with As⁺ ions in order to reduce the relaxation time. Trains of transform-limited laser pulses at 222 MHz as short as 410 fs centred at 1.99 µm were produced for the first time with a bulk Tm³⁺:Fluorogermanate glass. The maximum average output power obtained was of 84 mW. The same SESAM deployed on the Tm³⁺-Ho³⁺ Tellurite compounds gave trains of transform-limited pulses as short as 630 fs at 2.01 µm with a repetition rate of 143 MHz and a maximum averaged output power of 43 mW. The regime of propagation obtained was soliton-like and the modelocking was self-starting. The results obtained with bulk glass were very promising and open interesting research pathways within the realm of amorphous bulk gain media.

In this thesis, the development of a femtosecond Cr⁴⁺:forsterite solid-state laser is described where the mode-locking procedure was initiated using two novel saturable absorbers. One was a GaInNAs quantum-well device and the other a quantum-dot-based saturable absorber. These devices had not previously been exploited for the generation of femtosecond pulses from a solid-state laser but in the course of this project, successful mode-locked laser operation in the femtosecond domain was demonstrated for both devices. When the GaInNAs device was incorporated in the Cr⁴⁺:forsterite laser, transform-limited pulses with durations as short as 62fs were obtained. The performance of this femtosecond laser was significantly superior to that for previous quantum-well based saturable absorbers in the 1300nm spectral region. The dynamics of the device were investigated with the aim of refining subsequent devices and to explore the potential to grow future devices for use at longer wavelengths. At the outset of my research work quantum-dot based saturable absorbers had not be used for the mode locking of solid-state lasers in the femtosecond regime. The work presented in this thesis showed that quantum-dot structures could be exploited very effectively for this purpose. This was initially achieved with the quantum-dot element being inclined at an off-normal incidence within the cavity but experimental assessment together with further development of the device allowed for implementation at normal incidence. Reliable operation of the femtosecond laser was demonstrated very convincingly where transform-limited pulses of 160fs duration were generated. Having developed practical femtosecond Cr⁴⁺:forsterite lasers, the final part of the project research was directed towards exemplar applications for a laser operating in the 1300nm spectral region. These were biophotonics experiments in which assessments of both deep tissue penetration and two-photon chromosome cutting were undertaken. This work confirmed the suitability of the 1300nm laser radiation for propagation through substantial thicknesses of biological tissue (~15cm). The demonstration of highly localised two-photon cutting of Muntjac deer chromosomes also represented a novel result because single-photon absorption could be avoided effectively and the temporal broadening of the femtosecond pulses in the delivery optics arising from group velocity dispersion around 1300nm was minimal.

In this thesis two previously separate fields of study are brought together: optical micromanipulation and ultrashort laser research. Here, the benefits of combining the high peak powers of ultrashort pulsed lasers and conventional optical micromanipulation techniques are explored. As optical trapping has been studied extensively, the focus of this research is on optical guiding. Moreover, the emphasis is on the use of Bessel beams as these have been shown to offer greater guiding distances than comparable Gaussian beams. The studies within this thesis show that optical guiding in Bessel and Gaussian beams is governed by the average power of the laser. However, the benefits of guiding with ultrashort pulsed lasers to exploit multi-photon processes become evident as the demonstration of simultaneous optical guiding and second harmonic generation in microscopic nonlinear crystal fragments is detailed. This work is developed by using ultrashort pulses to induce two-photon excitation-induced fluorescence in the guiding medium. This allows direct visualisation of the beam-particle interaction and measurement of the reconstruction of the Bessel beam around an object. Some studies using two-photon excitation to investigate Bessel beam penetration through turbid media are discussed. Finally, the work is concluded by exploring the use of pulsed white-light lasers in optical guiding. The wavelength-dependent propagation and reconstruction properties of the white-light Bessel beam are studied before some preliminary optical guiding experiments are discussed. From this, the broad bandwidth of the supercontinuum source is found to offer extended guiding distances in Gaussian beams thereby negating the need for Bessel beams.

Doctor of Philosophy / Department of Physics / Itzhak Ben-Itzhak / Present laser technology allows for the production of ultra short (&7 fs) intense (.1016 W/cm2)pulses, which are comparable in duration and interaction strength to the vibrational period and the interaction that binds the electron in molecules, respectively. In this intense-field ultra short-pulse regime one can both measure and manipulate dynamics on the femtosecond timescale. To probe the dynamics of laser-matter interactions in this regime, we have chosen to start from the simplest possible molecule - H+ 2 , which can either dissociate into H + p or ionize into p + p + e. We have designed and employ a coincidence three-dimensional momentum imaging technique which allows us to measure ionization and dissociation of a molecular ion beam target simultaneously, while completely separating the two channels from each other. By varying the laser intensity and the pulse duration, we measure the intensity and pulse length dependent momentum distributions for laser induced fragmentation of H+ 2 at 790 nm. These dissociation measurements are in agreement with the phenomena predicted using the adiabatic Floquet picture, e.g. bond softening, in addition to more sophisticated calculations done by solving the time-dependent Schrodinger equation in the Born-Oppenheimer representation. Furthermore, the structure seen in ionization in our measurements and soon after by others is explained via a unified diabatic Floquet picture, which includes both ionization and dissociation in a single intensity and wavelength dependent picture that includes nuclear motion. Additionally, we use the same experimental techniques and apparatus to probe the laser-induced dynamics of multi-electron diatomic molecules, e.g. O+2, N+2, and ND+. The most probable dissociation and ionization pathways producing the features seen in these measurements are discerned using the angular and kinetic-energy-release distributions in conjunction with the diabatic Floquet picture. Finally, we extend these experimental techniques and interpretive models to the simplest polyatomic molecule - H+ 3 , whose fragmentation presents challenges both in our first-of-their-kind experiments and in physical interpretation.

Les impulsions laser de quelques cycles optiques offrent des capacités remarquables dans l’interaction laser-matière, en particulier pour l’ablation de matériaux diélectriques. Cependant, la focalisation d’impulsions laser ultracourtes dans l’air implique des limitations naturelles à la propagation linéaire du faisceau en amont de la cible. Dans ce contexte, on étudie l’ablation en surface de matériaux diélectriques lorsqu’ils sont irradiés par une impulsion unique de 12 fs dans l’air, dans des gammes d’intensités situées au-dessous et au-dessus de l’apparition des effets non linéaires dans l’air. En particulier, nous avons établi le lien entre la distribution en fluence en fonction des régimes de focalisation linéaire et non linéaire, et les diamètres des cratères. Nous avons démontré que le profil des cratères peut être prédit malgré les importantes modifications du faisceau laser à haute énergie, pour deux matériaux : la silice fondue et le saphir. Puis, après avoir identifié un régime d’ablation où le faisceau laser n’est pas affecté par ces effets non linéaires, nous avons développé un ensemble de diagnostics permettant de caractériser le plasma crée. Nous avons discuté et comparé les résultats obtenus sur les deux matériaux. En régime d’ablation, il apparaît alors que la densité du plasma est inférieure ou proche de la densité critique. De plus, la pénétration du faisceau est plus importante dans le cas du saphir que de la silice fondue donnant lieu à des cratères plus profonds. / Few-cycle laser pulses offer remarkable capabilities for laser-matter interaction, especially for ablation of transparent dielectric materials. However, focusing ultrashort laser pulses in air implies natural limitations to linear beam propagation prior the target. In this context, we study the surface ablation of dielectrics with single 12 fs laser pulses in air, at intensities below and above the apparition of nonlinear effects in air. In particular, we establish the link between the fluence distribution at the laser focus, spanning from linear- to nonlinear- focusing regimes, and the ablated crater diameters. We demonstrate that the crater profile can be predicted despite significant beam reshaping taking place at high fluence, for fused silica and sapphire. Then, we identify an ablation regime where the beam is still unaffected by nonlinear effects in air. In these conditions, we developed an energy balance experiment, allowing characterizing the created plasma. We discuss and compare the results acquired on fused silica and sapphire. We show that in ablation regime the density plasma is below or nearby the critical density. Moreover, the beam penetration is higher in sapphire than in fused silica, yielding deeper craters.

Neste trabalho investigamos a dinâmica de formação de nanopartículas de Au por pulsos de femtossegundos formatados (800 nm, 30 fs, 1 kHz e 2 mJ), induzida pela ionização da molécula de quitosana. Inicialmente desenvolvemos um sistema de formatação de pulsos ultracurtos que faz uso de um modulador espacial de luz, constituído por um arranjo linear de cristais líquidos, com o qual somos capazes de impor distintas modulações de fase ao pulso laser. Para monitorar o processo de produção de nanopartículas, montamos um sistema de excitação (pulsos de femtossegundos) e prova (luz branca), o qual permite a observação em tempo real do aparecimento da banda de plásmon e, consequentemente, da dinâmica de formação das nanopartículas. Resultados obtidos para pulsos não formatados (limitados por Transformada de Fourier) demonstraram que a formação de nanopartículas deve-se à ionização não linear da quitosana, a qual está relacionada à oxidação do grupo hidroxila para o grupo carbonila. Medidas de microscopia eletrônica de transmissão forneceram os tamanhos (entre 20 e 100 nm) e formatos (esferas, pirâmides, hexágonos, bastões, etc) das nanopartículas geradas. Ainda, nossos resultados revelaram que esta ionização é iniciada por absorção multifotônica, mais especificamente por absorção de 4 fótons. Utilizando pulsos formatados com fase espectrais constante, degrau e cossenoidal com diferentes frequências, investigamos a influência destes na formação de nanopartículas. Concluímos que os pulsos mais longos são mais favoráveis ao processo de ionização, e consequente redução dos íons de Au para a formação de nanopartículas metálicas. Este comportamento se deve, provavelmente, à redistribuição da energia absorvida para os modos vibracionais, o que é mais provável para pulsos mais longos. Assim, o método apresentado pode abrir novas maneiras para a formação de nanopartículas de metálicas, as quais podem ser mais exploradas dos pontos de vista aplicado e fundamental. / In this work we have studied the synthesis of Au nanoparticles using shaped ultrashort pulses (800 nm, 30 fs, 1 kHz and 2 mJ), induced by the ionization of the chitosan. Initially we developed a pulse shaping setup that uses a spatial light modulator (liquid crystals array), with which we are able to impose distinct phase mask to the laser pulse. In order to monitor the nanoparticles production process, we used a pump-probe system, consisting of femtosecond pulses (pump) and white light (probe), which allows the observation of the plasmon band enhancement and hence the nanoparticles formation dynamics. The results obtained by Fourier Transform limited pulses have shown that the nanoparticles formation is due to the nonlinear ionization of chitosan, which is related to hydroxyl group oxidation to the carbonyl group. Transmission electron microscopy measurements provided the sizes (20-100 nm) and shapes (spheres, pyramids, hexagons, rods, etc.) of the produced nanoparticles. Moreover, our results revealed that ionization is initiated by multiphoton absorption, more specifically by four photons absorption. Using pulses shaped with constant, step and cossenoidal (with different frequencies) spectral phase masks, we investigated their influence in the nanoparticles formation. We conclude that longer pulses are more favorable to the ionization process and, consequently, to the gold ions reduction for the synthesis of the metallic nanoparticles. This behavior is probably due to the redistribution of the absorbed energy to the vibrational modes, which is more likely for longer pulses. Therefore, the approach presented here can open new ways to produce metallic nanoparticles, which can be further explored from applied and fundamental points of view.