An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Étude par dynamique moléculaire de l'ablation par impulsions laser ultrabrèves de cibles nanocristallines

L’ablation de cibles d’Al nanocristallines (taille moyenne des cristallites d = 3,1 et 6,2 nm) par impulsions laser ultrabrèves (200 fs) a été étudiée par l’entremise de si- mulations combinant la dynamique moléculaire et le modèle à deux températures (two- temperature model, TTM) pour des fluences absorbées allant de 100 à 1300 J/m2. Nos simulations emploient un potentiel d’interaction de type EAM et les propriétés électro- niques des cibles en lien avec le TTM sont représentées par un modèle réaliste possédant une forme distincte dans le solide monocristallin, le solide nanocristallin et le liquide. Nous avons considéré l’effet de la taille moyenne des cristallites de même que celui de la porosité et nous avons procédé à une comparaison directe avec des cibles mono- cristallines. Nous avons pu montrer que le seuil d’ablation des métaux nanocristallins est significativement plus bas, se situant à 400 J/m2 plutôt qu’à 600 J/m2 dans le cas des cibles monocristallines, l’écart étant principalement dû à l’onde mécanique plus im- portante présente lors de l’ablation. Leur seuil de spallation de la face arrière est aussi significativement plus bas de par la résistance à la tension plus faible (5,40 GPa contre 7,24 GPa) des cibles nanocristallines. Il est aussi apparu que les contraintes résiduelles accompagnant généralement l’ablation laser sont absentes lors de l’ablation de cibles d’aluminium nanocristallines puisque la croissance cristalline leur permet d’abaisser leur volume spécifique. Nos résultats indiquent aussi que le seuil de fusion des cibles nano- cristallines est réduit de façon marquée dans ces cibles ce qui s’explique par la plus faible énergie de cohésion inhérente à ces matériaux. Nos simulations permettent de montrer que les propriétés structurelles et électroniques propres aux métaux nanocristallins ont toutes deux un impact important sur l’ablation.

Space and time characterization of laser-induced plasmas for applications in chemical analysis and thin film deposition

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz.

Ablation laser femtoseconde de verres métalliques de Cu_x Zr_(1−x) : une étude par dynamique moléculaire

L’ablation laser de verres métalliques de CuxZr1−x (x = 0.33, 0.50 et 0.67) et d’un alliage métallique cristallin de CuZr2 dans la structure C11b a été étudiée par dynamique moléculaire (DM) combinée à un modèle à deux températures (TTM). Le seuil d’ablation (Fth) a été déterminé pour chacun des 4 échantillons et s'est avéré plus bas pour les échantillons plus riches en Cu étant donné que la cohésion du Cu est plus faible que celle du Zr dans tous les échantillons. Pour x=0.33, Fth est plus bas pour le cristal que pour l’amorphe car le couplage électron-phonon est plus faible dans ce dernier, ce qui implique que l’énergie est transférée plus lentement du système électronique vers le système ionique pour le a-CuZr2 que le c-CuZr2. La vitesse de l’onde de pression créée par l’impact du laser croît avec la fluence dans l’échantillon cristallin, contrairement aux échantillons amorphes dans lesquels sa vitesse moyenne est relativement constante avec la fluence. Ceci est expliqué par le fait que le module de cisaillement croît avec la pression pour le cristal, ce qui n’est pas le cas pour les verres métalliques étudiés. Finalement, la zone affectée par la chaleur (HAZ) a été étudiée via la profondeur de fusion et les déformations plastiques. La plus faible température de fusion des échantillons amorphes implique que la profondeur de fusion est plus importante dans ceux-ci que dans l’échantillon cristallin. Dans les verres métalliques, les déformations plastiques ont été identifiées sous forme de zones de transformation par cisaillement (STZ) qui diffusent et fusionnent à plus haute fluence. Aucune déformation plastique importante n’a été identifiée dans le c-CuZr2 mis à part de légères déformations près du front de fusion causées par les contraintes résiduelles. Ce travail a ainsi permis d’améliorer notre compréhension de l’ablation laser sur les verres métalliques et de l’étendue des dommages qu’elle peut entraîner.

Nonlinear Dynamics of Semiconductor LasersControl and Synchronization of Chaos:

Nonlinear dynamics of laser systems has become an interesting area of research in recent times. Lasers are good examples of nonlinear dissipative systems showing many kinds of nonlinear phenomena such as chaos, multistability and quasiperiodicity. The study of these phenomena in lasers has fundamental scientific importance since the investigations on these effects reveal many interesting features of nonlinear effects in practical systems. Further, the understanding of the instabilities in lasers is helpful in detecting and controlling such effects. Chaos is one of the most interesting phenomena shown by nonlinear deterministic systems. It is found that, like many nonlinear dissipative systems, lasers also show chaos for certain ranges of parameters. Many investigations on laser chaos have been done in the last two decades. The earlier studies in this field were concentrated on the dynamical aspects of laser chaos. However, recent developments in this area mainly belong to the control and synchronization of chaos. A number of attempts have been reported in controlling or suppressing chaos in lasers since lasers are the practical systems aimed to operated in stable or periodic mode. On the other hand, laser chaos has been found to be applicable in high speed secure communication based on synchronization of chaos. Thus, chaos in laser systems has technological importance also. Semiconductor lasers are most applicable in the fields of optical communications among various kinds of laser due to many reasons such as their compactness, reliability modest cost and the opportunity of direct current modulation. They show chaos and other instabilities under various physical conditions such as direct modulation and optical or optoelectronic feedback. It is desirable for semiconductor lasers to have stable and regular operation. Thus, the understanding of chaos and other instabilities in semiconductor lasers and their xi control is highly important in photonics. We address the problem of controlling chaos produced by direct modulation of laser diodes. We consider the delay feedback control methods for this purpose and study their performance using numerical simulation. Besides the control of chaos, control of other nonlinear effects such as quasiperiodicity and bistability using delay feedback methods are also investigated. A number of secure communication schemes based on synchronization of chaos semiconductor lasers have been successfully demonstrated theoretically and experimentally. The current investigations in these field include the study of practical issues on the implementations of such encryption schemes. We theoretically study the issues such as channel delay, phase mismatch and frequency detuning on the synchronization of chaos in directly modulated laser diodes. It would be helpful for designing and implementing chaotic encryption schemes using synchronization of chaos in modulated semiconductor laser

Studies on the Effect of Randomness on the Synchronization of Coupled Systems and on the Dynamics of Intermittently driven systems

Nonlinear dynamics has emerged into a prominent area of research in the past few Decades.Turbulence, Pattern formation,Multistability etc are some of the important areas of research in nonlinear dynamics apart from the study of chaos.Chaos refers to the complex evolution of a deterministic system, which is highly sensitive to initial conditions. The study of chaos theory started in the modern sense with the investigations of Edward Lorentz in mid 60's. Later developments in this subject provided systematic development of chaos theory as a science of deterministic but complex and unpredictable dynamical systems. This thesis deals with the effect of random fluctuations with its associated characteristic timescales on chaos and synchronization. Here we introduce the concept of noise, and two familiar types of noise are discussed. The classifications and representation of white and colored noise are introduced. Based on this we introduce the concept of randomness that we deal with as a variant of the familiar concept of noise. The dynamical systems introduced are the Rossler system, directly modulated semiconductor lasers and the Harmonic oscillator. The directly modulated semiconductor laser being not a much familiar dynamical system, we have included a detailed introduction to its relevance in Chaotic encryption based cryptography in communication. We show that the effect of a fluctuating parameter mismatch on synchronization is to destroy the synchronization. Further we show that the relation between synchronization error and timescales can be found empirically but there are also cases where this is not possible. Studies show that under the variation of the parameters, the system becomes chaotic, which appears to be the period doubling route to chaos.

Characterization and Imaging Diagnostics of Laser Induced Plasma from Solid Targets

Laser induced plasma (LIP) emissions from some metal oxide targets were studied with corresponding metal targets of pure quality as a reference. Atomic emissions in the visible region were used in the spectroscopic procedures of LIP characterization. The studies were meant to throw light into LIP dynamics and they provided many experimental results which improved the general awareness of plasma state.When target materials were photo-ablated with an energetically suitable laser pulse, they developed electric charges in them.An electrical signal which was delivered from the target served as an alternative probe signal for the diagnostics of LIP and to track different charged states in the plasma. The signal showed a double peak distribution with positive polarity and a modified time of flight with various voltage levels of a given polarity.The expansion dynamics of LIP in magnetic field were also investigated by monitoring the voltage transients generated at the target.

Nonlinear Dynamics of Nd:YAG lasers: Hopf bifurcation, Multistability and Chaotic Synchronization

In this thesis we have presented some aspects of the nonlinear dynamics of Nd:YAG lasers including synchronization, Hopf bifurcation, chaos control and delay induced multistability.We have chosen diode pumped Nd:YAG laser with intracavity KTP crystal operating with two mode and three mode output as our model system.Different types of orientation for the laser cavity modes were considered to carry out the studies. For laser operating with two mode output we have chosen the modes as having parallel polarization and perpendicular polarization. For laser having three mode output, we have chosen them as two modes polarized parallel to each other while the third mode polarized orthogonal to them.

Fast imaging of laser-blow-off plume:Lateral confinement in ambient environment

The dynamics of plasma plume, formed by the laser-blow-off of multicomponent LiF-C thin film under various ambient pressures ranging from high vacuum to argon pressure of 3 Torr, has been studied using fast imaging technique. In vacuum, the plume has ellipsoidal shape. With the increase in the ambient pressure, sharp plume boundary is developed showing a focusing-like confinement in the lateral space behavior in the front end, which persists for long times. At higher ambient pressure (> 10−1 Torr ), structures are developed in the plasma plume due to hydrodynamic instability/turbulences.

Influence of ambient gas on the temperature and density of laser produced carbon plasma

The effect of ambient gas on the dynamics of the plasma generated by laser ablation of a carbon target using 1.06 μm radiation from a Q-switched Nd:YAG laser has been investigated using a spectroscopic technique. The emission characteristics of the carbon plasma produced in argon, helium and air atmospheres are found to depend strongly on the nature and pressure of the surrounding gas. It has been observed that hotter and denser plasmas are formed in an argon atmosphere rather than in helium or air as an ambient.

Collective behavior of laser-produced plasma from a multicomponent YBa2Cu3O7 target in air

The dynamics of diffusion of electrons and ions from the laser-produced plasma from a multielement superconducting material, namely YBa2Cu3O7, using a Q-switched Nd:YAG laser is investigated by time-resolved emission-spectroscopic techniques at various laser irradiances. It is observed that beyond a laser irradiance of 2.6 \xC3\x97 1011 W cm-2, the ejected plume collectively drifts away from the target with a sharp increase in velocity to 1.25 \xC3\x97 106 cm s-1, which is twice its velocity observed at lower laser irradiances. This sudden drift apparently occurs as a result of the formation of a charged double layer at the external plume boundary. This diffusion is collective, that is, the electrons and ions inside the plume diffuse together simultaneously and hence it is similar to the ambipolar diffusion of charged particles in a discharge plasma

Temporal and spatial evolution of C2 in laser induced plasma from graphite target

Laser ablation of graphite has been carried out using 1.06mm radiation from a Q-switched Nd:YAG laser and the time of flight distribution of molecular C2 present in the resultant plasma is investigated in terms of distance from the target as well as laser fluences employing time resolved spectroscopic technique. At low laser fluences the intensities of the emission lines from C2 exhibit only single peak structure while beyond a threshold laser fluence, emission from C2 shows a twin peak distribution in time. The occurrence of the faster velocity component at higher laser fluences is explained as due to species generated from recombination processes while the delayed peak is attributed to dissociation of higher carbon clusters resulting in the generation of C2 molecule. Analysis of measured data provides a fairly complete picture of the evolution and dynamics of C2 species in the laser induced plasma from graphite.

Fine structure in the time of flight distribution of C2 in laser produced plasma from graphite

Time resolved optical emission spectroscopy is employed to study the expansion dynamics of C2 species in a graphite plasma produced during the Nd : YAG ablation. At low laser fluences a single peak distribution with low kinetic energy is observed. At higher fluences a twin peak distribution is found. It has been noted that these double peak time of flight distribution splits into a triple peak structure at distances >_ 17mm from the target surface. The reason for the occurrence of multiple peak is due to different formation mechanisms of C2 species

Studies on Laser Induced and RF Sputtered Plasma using Optical Emission Spectroscopy and Langmuir Probe

The main objective of the present study is to understand different mechanisms involved in the production and evolution of plasma by the pulsed laser ablation and radio frequency magnetron sputtering. These two methods are of particular interest, as these are well accomplished methods used for surface coatings, nanostructure fabrications and other thin film devices fabrications. Material science researchers all over the world are involved in the development of devices based on transparent conducting oxide (TCO) thin films. Our laboratory has been involved in the development of TCO devices like thin film diodes using zinc oxide (ZnO) and zinc magnesium oxide (ZnMgO), thin film transistors (TFT's) using zinc indium oxide and zinc indium tin oxide, and some electroluminescent (EL) devices by pulsed laser ablation and RF magnetron sputtering.In contrast to the extensive literature relating to pure ZnO and other thin films produced by various deposition techniques, there appears to have been relatively little effort directed towards the characterization of plasmas from which such films are produced. The knowledge of plasma dynamics corresponding to the variations in the input parameters of ablation and sputtering, with the kind of laser/magnetron used for the generation of plasma, is limited. To improve the quality of the deposited films for desired application, a sound understanding of the plume dynamics, physical and chemical properties of the species in the plume is required. Generally, there is a correlation between the plume dynamics and the structural properties of the films deposited. Thus the study of the characteristics of the plume contributes to a better understanding and control of the deposition process itself. The hydrodynamic expansion of the plume, the composition, and SIze distribution of clusters depend not only on initial conditions of plasma production but also on the ambient gas composition and pressure. The growth and deposition of the films are detennined by the thermodynamic parameters of the target material and initial conditions such as electron temperature and density of the plasma.For optimizing the deposition parameters of various films (stoichiometric or otherwise), in-situ or ex-situ monitoring of plasma plume dynamics become necessary for the purpose of repeatability and reliability. With this in mind, the plume dynamics and compositions of laser ablated and RF magnetron sputtered zinc oxide plasmas have been investigated. The plasmas studied were produced at conditions employed typically for the deposition of ZnO films by both methods. Apart from this two component ZnO plasma, a multi-component material (lead zirconium titanate) was ablated and plasma was characterized.

Hopf bifurcation in parallel polarized Nd:YAG laser

Dynamics of Nd:YAG laser with intracavity KTP crystal operating in two parallel polarized modes is investigated analytically and numerically. System equilibrium points were found out and the stability of each of them was checked using Routh–Hurwitz criteria and also by calculating the eigen values of the Jacobian. It is found that the system possesses three equilibrium points for (Ij, Gj), where j = 1, 2. One of these equilibrium points undergoes Hopf bifurcation in output dynamics as the control parameter is increased. The other two remain unstable throughout the entire region of the parameter space. Our numerical analysis of the Hopf bifurcation phenomena is found to be in good agreement with the analytical results. Nature of energy transfer between the two modes is also studied numerically.