Doctor of Philosophy / Department of Physics / Uwe Thumm / Although the latest and most powerful supercomputer today, Tianhe-2 in China, can finish 33.86 quadrillion floating-point operations per second (www.top500.org), it is still a big challenge to simulate the simplest few-electron system - the helium atom - a threebody system with one nucleus and two electrons. Within the fixed-nucleus approximation and time-dependent close coupling (TDCC) approach, we developed software to solve the time-dependent Schrödinger equation (TDSE) accurately, implementing the finite-element discrete-variable representation (FE-DVR) scheme. The general idea of the method is to expand the wave functions in the eigenvectors of the angular momentum operator, which further transform the six-dimensional TDSE to a set of infinite two-dimensional coupled equations. Although there are infinitely many coupled equations, they can be truncated to a finite number of equations by applying selection rules and physical requirements, and solved with our current computational resources. By numerically solving the TDSE in full dimensionality, we investigate the double photoionization of helium atoms in external fields. In co-planar emission geometry with and without the presence of a comparatively weak infrared (IR) laser pulse, we discuss the double ionization (DI) dynamics of helium atoms irradiated by ultrashort pulses of extreme ultraviolet (XUV) laser light. We first investigate the degree of electronic correlation by correlated photoelectron angular distributions for two-photon double ionization (TPDI) of helium atoms in the sequential and non-sequential DI regime. We quantify sequential and non-sequential contributions to TPDI driven by an XUV pulse with central photon energy hw[subscript]xuv near the sequential DI threshold. If the spectral width of the XUV pulse is broad enough, both the sequntial (hw[subscript]xuv > 54.4 eV) and non-sequential (hw[subscript]xuv < 54.4 eV) channels are open. Therefore, the sequential and non-sequential DI mechanisms are difficult to distinguish. By tracking the DI asymmetry in joint photoelectron angular distributions, we introduce the forward-backward-emission asymmetry as a measure that allows the distinction of sequential and non-sequential contributions. Specifically, for hw[subscript]xuv = 50 eV pulses with a sine-squared temporal profile, we find that the sequential DI contribution is the largest at a pulse length of 650 as (1 as = 10[superscript]−18 s), due to competing temporal and spectral constraints. In addition, we validate a simple heuristic expression for the sequential DI contribution in comparison with ab initio calculations. We then investigate the influence of the laser field on the DI of helium by a single XUV pulse. For IR-laser-assisted single-XUV-photon DI our joint angular distributions show that the IR-laser field enhances back-to-back electron emission and induces a characteristic splitting in the angular distribution for electrons that are emitted symmetrically relative to the identical linear polarization directions of the XUV and IR pulse. These IR-pulse-induced changes in photoelectron angular distributions are (i) imposed by different symmetry constraints for XUV-pulse-only and laser-assisted XUV-photon DI, (ii) robust over a large range of energy sharing between the emitted electrons, and (iii) consistent with the transfer of discrete IR-photon momenta to both photoelectrons from the assisting IR-laser field. While selection-rule forbidden at equal energy sharing, for increasingly unequal energy sharing we find back-to-back emission to become more likely and to compete with symmetric emission. To obtain a high level of accuracy, accurate quantum-mechanical calculations of three Coulomb interacting particales exposed to an intense XUV and weak IR field are at the limit of current computational power. Any direct extension (such as strong laser-field intensity, elliptically-polarized field, and laser-induced DI) of our approach to more complicated systems appears to be currently out of reach. At the end of this thesis, we give suggestions on how to improve the efficiency of TDSE calculations for simulations of these complicated many-photon processes.

The adiabatic approximation is a natural approach for the description of phenomena induced by low frequency laser radiation because the ratio of the laser frequency to the characteristic frequency of an atom or a molecule is a small parameter. Since the main aim of this work is the study of ionization phenomena, the version of the adiabatic approximation that can account for the transition from a bound state to the continuum must be employed. Despite much work in this topic, a universally accepted adiabatic approach of bound-free transitions is lacking. Hence, based on Savichev's modified adiabatic approximation [Sov. Phys. JETP 73, 803 (1991)], we first of all derive the most convenient form of the adiabatic approximation for the problems at hand. Connections of the obtained result with the quasiclassical approximation and other previous investigations are discussed. Then, such an adiabatic approximation is applied to single-electron ionization and non-sequential double ionization of atoms in a strong low frequency laser field. The momentum distribution of photoelectrons induced by single-electron ionization is obtained analytically without any assumptions on the momentum of the electrons. Previous known results are derived as special cases of this general momentum distribution. The correlated momentum distribution of two-electrons due to non-sequential double ionization of atoms is calculated semi-analytically. We focus on the deeply quantum regime -- the below intensity threshold regime, where the energy of the active electron driven by the laser field is insufficient to collisionally ionize the parent ion, and the assistance of the laser field is required to create a doubly charged ion. A special attention is paid to the role of Coulomb interactions in the process. The signatures of electron-electron repulsion, electron-core attraction, and electron-laser interaction are identified. The results are compared with available experimental data. Two-electron correlated spectra of non-sequential double ionization below intensity threshold are known to exhibit back-to-back scattering of the electrons, viz., the anticorrelation of the electrons. Currently, the widely accepted interpretation of the anticorrelation is recollision-induced excitation of the ion plus subsequent field ionization of the second electron. We argue that there exists another mechanism, namely simultaneous electron emission, when the time of return of the rescattered electron is equal to the time of liberation of the bounded electron (the ion has no time for excitation), that can also explain the anticorrelation of the electrons in the deep below intensity threshold regime. Finally, we study single-electron molecular ionization. Based on the geometrical approach to tunnelling by P. D. Hislop and I. M. Sigal [Memoir. AMS 78, No. 399 (1989)], we introduce the concept of a leading tunnelling trajectory. It is then proven that leading tunnelling trajectories for single active electron models of molecular tunnelling ionization (i.e., theories where a molecular potential is modelled by a single-electron multi-centre potential) are linear in the case of short range interactions and ``almost'' linear in the case of long range interactions. The results are presented on both the formal and physically intuitive levels. Physical implications of the proven statements are discussed.

The adiabatic approximation is a natural approach for the description of phenomena induced by low frequency laser radiation because the ratio of the laser frequency to the characteristic frequency of an atom or a molecule is a small parameter. Since the main aim of this work is the study of ionization phenomena, the version of the adiabatic approximation that can account for the transition from a bound state to the continuum must be employed. Despite much work in this topic, a universally accepted adiabatic approach of bound-free transitions is lacking. Hence, based on Savichev's modified adiabatic approximation [Sov. Phys. JETP 73, 803 (1991)], we first of all derive the most convenient form of the adiabatic approximation for the problems at hand. Connections of the obtained result with the quasiclassical approximation and other previous investigations are discussed. Then, such an adiabatic approximation is applied to single-electron ionization and non-sequential double ionization of atoms in a strong low frequency laser field. The momentum distribution of photoelectrons induced by single-electron ionization is obtained analytically without any assumptions on the momentum of the electrons. Previous known results are derived as special cases of this general momentum distribution. The correlated momentum distribution of two-electrons due to non-sequential double ionization of atoms is calculated semi-analytically. We focus on the deeply quantum regime -- the below intensity threshold regime, where the energy of the active electron driven by the laser field is insufficient to collisionally ionize the parent ion, and the assistance of the laser field is required to create a doubly charged ion. A special attention is paid to the role of Coulomb interactions in the process. The signatures of electron-electron repulsion, electron-core attraction, and electron-laser interaction are identified. The results are compared with available experimental data. Two-electron correlated spectra of non-sequential double ionization below intensity threshold are known to exhibit back-to-back scattering of the electrons, viz., the anticorrelation of the electrons. Currently, the widely accepted interpretation of the anticorrelation is recollision-induced excitation of the ion plus subsequent field ionization of the second electron. We argue that there exists another mechanism, namely simultaneous electron emission, when the time of return of the rescattered electron is equal to the time of liberation of the bounded electron (the ion has no time for excitation), that can also explain the anticorrelation of the electrons in the deep below intensity threshold regime. Finally, we study single-electron molecular ionization. Based on the geometrical approach to tunnelling by P. D. Hislop and I. M. Sigal [Memoir. AMS 78, No. 399 (1989)], we introduce the concept of a leading tunnelling trajectory. It is then proven that leading tunnelling trajectories for single active electron models of molecular tunnelling ionization (i.e., theories where a molecular potential is modelled by a single-electron multi-centre potential) are linear in the case of short range interactions and ``almost'' linear in the case of long range interactions. The results are presented on both the formal and physically intuitive levels. Physical implications of the proven statements are discussed.

Une étude théorique et expérimentale sur la simple et double ionisation de petites molécules par impact électronique a été effectuée dans le présent travail. Des expériences de simple ionisation des trois orbitales de valence de l'ammoniac pour une énergie incidente de l'ordre de 600 eV ont été réalisées à Orsay (ISMO). Ces expériences, notées (e,2e), consistent à détecter les électrons diffusé et éjecté en coïncidence. Nous avons comparé les expériences correspondantes à des théories perturbatrices telles que la première approximation de Born : 1CW (One Coulomb Wave) et 1DW (One Distorted Wave). Ainsi que le modèle BBK (pour l'acronyme Brauner, Briggs and Klar). Nos résultats ont montré un accord raisonnable entre l'expérience et la théorie en ce qui concerne la distribution du lobe binaire. Par contre, le lobe de recul est largement sous-estimé. L'application du modèle BBK incluant la prise en compte des déphasages à courte portée est une intéressante perspective pour la description de l'ionisation simple de la molécule d'ammoniac. De même, nous avons étudié les processus d'ionisation du méthane par impact d'électrons. Pour la simple ionisation du méthane, nous avons fourni des approches théoriques pour décrire la distribution angulaire des sections efficaces doublement et triplement différentielle. Nos résultats ont été comparés aux expériences réalisées à Afyon en Turquie. Pour la double ionisation du méthane, nous avons réalisé des expériences (e,3-1e) (dans laquelle l'électron diffusé et un des éjectés sont détectés en coïncidence) pour la couche externe 1t2 à Orsay (ISMO). La théorie que nous avons appliquée est du premier ordre et ne peut pas décrire complétement les deux lobes. Par conséquent, le développement d'un modèle dans le cadre de la deuxième approximation de Born s'avère nécessaire. / A theoretical and experimental study on simple and double ionization of small molecules by electron impact is reported in the present work. Experiments of simple ionization of the three valence orbitals of ammonia with an incident energy of about 600 eV were performed in Orsay (ISMO). These experiments, named (e,2e), consist in the detection of the scattered and ejected electrons in coincidence. We compared the correspondent experiments to perturbative theories such as first Born approximation: 1CW (One Coulomb Wave) and 1DW (One Distorted Wave). In addition to the BBK model (for the acronym Brauner, Briggs and Klar). Our results show a reasonable agreement between the experiment and the theory concerning the distribution of the binary lobe. On the contrary, the recoil lobe was largely under-estimated. The application of the BBK model by taking into account the short range phases will be an interesting perspective for the description of simple ionization of ammonia molecule. In addition, we studied the ionization process of methane by electron impact. For the simple ionization of methane, we developed theoretical approaches in order to describe the angular distribution of double and triple differential cross sections. Our results were compared to experimental data performed in Afyon in Turkey. For the double ionization of methane, we performed experiments for the external shell 1t2 in Orsay (ISMO) by using the (e,3-1e), during which the scattered and one of the two ejected electrons are detected in coincidence. The theory which we applied is of first order and it could not describe completely the two lobes. Consequently, the development of a second order model sounds necessary.

Etude théorique de l'interaction entre un atome à deux ou trois électrons actifs et un champ laser de fort éclairement (10^13 à 10^15 W.cm-2) et de durée d'impulsion ultra-brève (femto à attoseconde) dans le domaine spectral XUV. Notre approche est basée sur la résolution de l'équation de Schrödinger dépendante du temps. L'impulsion laser est définie par un modèle semi-classique. Les fonctions d'onde sont construites en utilisant des B-splines. Nous étudions particulièrement la double ionisation à deux photons de l'hélium dans l'état fondamental ainsi que dans l'état excité 1s2s. Nous testons une méthode d'approximation pour traiter certains ions héliumoÏdes. Enfin nous abordons le Lithium, système à trois électrons actifs. Nous comparons la double ionisation à deux photons par voie séquentielle et directe avec He(1s2s) dont la structure asymétrique est proche de celle du lithium. / Theoretical study of the interaction between an atom and a two or three electron system with an ultra short (10^-15 to 10^-18 s) high intensity (10^13 à 10^15 W.cm-2) pulse in the XUV domain. Our approach is based on the solving of th time dependent Schrödinger equation. Laser pulse is defined by a semi classical model. Wave functions are built with B-splines.We study particularly helium two photons double ionization in fundamental and excited state 1s2s. Then we test an approximative method to treat helium-like ions.At last, we investigate lithium, a three active electrons system. We compare TPDI in sequential and direct channel with He(1s2s) which asymmetric structure looks like Li's one.

Orientador: Rogério Custodio / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T05:01:18Z (GMT). No. of bitstreams: 1 Streit_Livia_D.pdf: 1852639 bytes, checksum: 1d6bd6190d21b329d992dfe5f74f8993 (MD5) Previous issue date: 2012 / Resumo: O estudo de processos fotoeletrônicos, como energias de dupla ionização é de grante interesse teórico e experimental na área da física molecular. Cálculos e medidas experimentais de energias de dupla ionização e de energias de ligação de elétron envolvem o entendimento de correlação e relaxação eletrônica. A consideração de tais efeitos é indispensável para a obtenção de resultados precisos. No presente trabalho, tais processos fotoeletrônicos são estudados com métodos Pós-Hartree-Fock e Monte Carlo Quântico (MCQ). No último caso, o método foi adaptado de maneira a utilizar um tipo diferente de função de onda. A primeira parte desta tese envolve o estudo de energias de dupla ionização. O objetivo prinicipal é a análise do tipo de função de onda tentativa no método MCQ. Três diferentes formas foram estudadas: Uma função Hartree-Fock monodeterminante com uma função de correlação eletrônica explícita de Boys-Handy otimizada para a molécula; uma função CI multideterminante; e ainda, uma função de onda multideterminante construída a partir de orbitais de Dyson. Para obter a função de onda de Dyson, um extenso trabalho envolvendo estudo e programação do programa de cálculo de estrutura eletrônica Gaussian 09 foi necessário. A primeira parte da tese ainda envolve o estudo de energias de dupla ionização por métodos Interação de Configurações Multireferência MRCI e Gaussian-3 G3. Os resultados obtidos são comparados aos resultados obtidos por MCQ. A segunda parte da tese compreende o estudo de energias de ligação de elétron de complexos de gases nobres com o ânion Uracila. A coexistência de ânions em que o orbital singularmente ocupado apresenta características de um orbital de valência e de um orbital muito difuso é investigada através de análise de geometria e do cálculo de energias de afinidade eletrônica e de ligação de elétron dos complexos neutros e aniônicos / Abstract: The study of photoelectron processes such as double ionization energies has become a very interesting field in experimental and theoretical molecular physics. Calculation and experimental measure of double ionization energies and electron binding energies involve understanding of electron correlation and relaxation energies. Consideration of those effects are a requisite in order to predict precise values. In this work, those photoelectron processes are studied with post-Hartree-Fock and Quantum Monte Carlo (QMC) methods. In the latter case, the method was also modified to take in account a different type of wavefunction. The first part of this thesis is concerned with the study of double ionization energies. The main objective of this work is the analysis of the type of trial wavefunction in QMC method. Three different forms were studied: A single determinant Hartree-Fock function, with the Boys-Handy explicit electron correlation function optimized for the molecule; a multi-determinant CI wavefunction; and finally, a multi-determinant wavefunction built from Dyson orbitals. In order to obtain the Dyson wavefunction, an extensive work on studying and programming the electron structure package Gaussian 09 was necessary. The first part still comprises the study of double ionization energies with MRCI and G3 methods. The results thus obtained were compared to the QMC results. The second part of this thesis embraces the study of electron binding energies of uracil¿noble-gas complexes. The coexistence of valence and diffuse¿bound anions of U(Xe), suggested by experimental studies is investigated with geometry analysis and calculation of adiabatic electron affinities and vertical electron detachment energies of the neutral an anionic complexes / Doutorado / Físico-Química / Doutor em Ciências

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In this work, different double ionization (DI) mechanisms of various atomic and molecular targets by electron impact at different intermediate incident energies have been studied by so-called (e, 3-1e) and (e, 3e) experiments. Four and five fold differential cross sections in angle and in energy have been measured and analyzed in a coplanar geometry. The experimental measurements are compared with both first order and second order theoretical model calculations. The results shows that the theories including second order mechanism (such as Two Step 2, TS2) are generally in better agreement with the experimental data than these only including first order mechanisms (such as Shake Off and Two Step 1). This demonstrates that under present kinematics, second order mechanism plays an important role or even dominates over first order mechanisms. Besides, all DI results are compared with the predictions of TS2 kinematical analysis developed by Lahmam-Bennani et al (2010). Most of the structures shown in the measured angular distribution can be correctly explained by the TS2 kinematical analysis predictions. Besides, we extend this model by including the recoil contribution in each step. Some structures which cannot be explained by the previous model are well explained by the extended TS2 kinematical model. The isoelectronic target structure influence in DI is investigated preliminarily. The (e, 3-1e) results on Ne and CH₄ indicate the differences under same kinematics. The data analysis is underway.

The multiconfiguration time-dependent Hartree-Fock (MCTDHF) and multiconfiguration time-dependent Hartree (MCTDH) methods are employed to investigate nonperturbative multielectron dynamics in finite quantum systems. MCTDHF is a powerful tool that allows for the investigation of multielectron dynamics in strongly perturbed quantum systems. We have developed an MCTDHF code that is capable of treating problems involving three dimensional (3D) atoms and molecules exposed to strong laser fields. This code will allow for the theoretical treatment of multielectron phenomena in attosecond science that were previously inaccessible. These problems include complex ionization processes in pump-probe experiments on noble gas atoms, the nonlinear effects that have been observed in Ne atoms in the presence of an x-ray free-electron laser (XFEL) and the molecular rearrangement of cations after ionization. An implementation of MCTDH that is optimized for two electrons, each moving in two dimensions (2D), is also presented. This implementation of MCTDH allows for the efficient treatment of 2D spin-free systems involving two electrons; however, it does not scale well to 3D or to systems containing more that two electrons. Both MCTDHF and MCTDH were used to treat 2D problems in nanophysics and attosecond science. MCTDHF is used to investigate plasmon dynamics and the quantum breathing mode for several electrons in finite lateral quantum dots. MCTDHF is also used to study the effects of manipulating the potential of a double lateral quantum dot containing two electrons; applications to quantum computing are discussed. MCTDH is used to examine a diatomic model molecular system exposed to a strong laser field; nonsequential double ionization and high harmonic generation are studied and new processes identified and explained. An implementation of MCTDHF is developed for nonuniform tensor product grids; this will allow for the full 3D implementation of MCTDHF and will provide a means to investigate a wide variety of problems that cannot be currently treated by any other method. Finally, the time it takes for an electron to tunnel from a bound state is investigated; a definition of the tunnel time is established and the Keldysh time is connected to the wavefunction dynamics.

The multiconfiguration time-dependent Hartree-Fock (MCTDHF) and multiconfiguration time-dependent Hartree (MCTDH) methods are employed to investigate nonperturbative multielectron dynamics in finite quantum systems. MCTDHF is a powerful tool that allows for the investigation of multielectron dynamics in strongly perturbed quantum systems. We have developed an MCTDHF code that is capable of treating problems involving three dimensional (3D) atoms and molecules exposed to strong laser fields. This code will allow for the theoretical treatment of multielectron phenomena in attosecond science that were previously inaccessible. These problems include complex ionization processes in pump-probe experiments on noble gas atoms, the nonlinear effects that have been observed in Ne atoms in the presence of an x-ray free-electron laser (XFEL) and the molecular rearrangement of cations after ionization. An implementation of MCTDH that is optimized for two electrons, each moving in two dimensions (2D), is also presented. This implementation of MCTDH allows for the efficient treatment of 2D spin-free systems involving two electrons; however, it does not scale well to 3D or to systems containing more that two electrons. Both MCTDHF and MCTDH were used to treat 2D problems in nanophysics and attosecond science. MCTDHF is used to investigate plasmon dynamics and the quantum breathing mode for several electrons in finite lateral quantum dots. MCTDHF is also used to study the effects of manipulating the potential of a double lateral quantum dot containing two electrons; applications to quantum computing are discussed. MCTDH is used to examine a diatomic model molecular system exposed to a strong laser field; nonsequential double ionization and high harmonic generation are studied and new processes identified and explained. An implementation of MCTDHF is developed for nonuniform tensor product grids; this will allow for the full 3D implementation of MCTDHF and will provide a means to investigate a wide variety of problems that cannot be currently treated by any other method. Finally, the time it takes for an electron to tunnel from a bound state is investigated; a definition of the tunnel time is established and the Keldysh time is connected to the wavefunction dynamics.