A theoretical model describing photophysics of π-conjugated aggregates, such as molecular crystals and polymer thin films, is developed. A Holstein-like Hamiltonian expressed with a multi-particle basis set is used to evaluate absorption and photoluminescence (PL) spectra. An analysis with line strength ratio proves to be a powerful diagnostic tool to obtain additional spectral signatures with which to distinguish H- vs. J-aggregation. For the H-aggregates absorption peak ratio, A0-0/A0-1, diminishes as the excitonic coupling increases. Also the PL peak ratio, I0-0/I0-1, is zero at T=0K with no disorder and the value increases as temperature and disorder increase. By contrast the J-aggregates show the opposite trends. Furthermore we will show the PL peak ratio provides a direct measurement of the exciton coherence length for a linear J-aggregate and could be expressed as I0-0/I0-1 = Ncoh/l2. We will also show that it is inversely proportional to square root of temperature (T-1/2). Applying our theory to the herringbone style oligoacene molecular crystals, we show the lowest singlet exciton states are highly influenced by charge transfer (CT) states and the well known energetic gap in two polarized absorption spectra, so called Davydov Splitting (DS), is a product of the interaction. We have successfully reproduced the DS for all three oligoacenes without any free parameters. Inspired by the CT contribution in oligoacene crystals, we further develop Wannier-Mott exciton model and apply to disorder-free polydiacetylene (PDA) quantum wires, which have been shown to be extremely emissive. We will show the quantum wire is a J-aggregate and we once again derive the peak ratio and the coherence size relation, I0-0/I0-1 = kNcoh/l2, where k is a prefactor close to unity. Typical photophysical properties of polymer p-stacks such as those occurring in P3HT films are well explained by the simple linear H-aggregate model. However several groups have started seeing more J-like behaviors amongst “improved” (less disordered) polymer films such as increased values of A0-0/A0-1 and I0-0/I0-1 and higher radiative rates. With the new perception of a single polymer chain being a J-aggregate, we apply our new theory to p-stack of polymer chains. We call this HJ-aggregate model since the interchain interaction induces H-aggregation. In the study we show a competition between intrachain and interchain interactions that leads to unique photophysical features. The new model is capable of explaining a wide range of polymer systems and most importantly the theory uncovers the mechanism of the improved polymer films; reducing disorder urges increasing intrachain reactions within each chain, thus enhancing more J-like spectral features. / Chemistry

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25014号 / 工博第5191号 / 新制||工||1991(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 徹, 教授 田中 庸裕, 教授 佐藤 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

This work presents a new implementation of the QP algorithm, a computer method to diagonalize the extremely large matrices arising in multimode vibronic problems. Benchmark calculations are included, showing the accuracy of the program. The QP algorithm is extended to treat multiple electronic surfaces for competitive control and this is demonstrated with an Hamiltonian including three electronic states, a model of the benzene radical cation. Finally, the evolution of zeroth-order states in a simple two electronic states, two dimensional model with a conical intersection is explored, towards building a time-dependent view of overlapping resonances coherent control.

This work presents a new implementation of the QP algorithm, a computer method to diagonalize the extremely large matrices arising in multimode vibronic problems. Benchmark calculations are included, showing the accuracy of the program. The QP algorithm is extended to treat multiple electronic surfaces for competitive control and this is demonstrated with an Hamiltonian including three electronic states, a model of the benzene radical cation. Finally, the evolution of zeroth-order states in a simple two electronic states, two dimensional model with a conical intersection is explored, towards building a time-dependent view of overlapping resonances coherent control.

We studied the effects of underdamped vibrational modes on excitonic energy transfer in small molecular aggregates by means of ultrafast nonlinear spectroscopy. We developed a vibronic dynamical model to account for the interplay of electronic and vibrational coherence during excitation transport. Our model was aimed to simulate signals of a broad class of linear and third order spectroscopies (absorption, fluorescence, transient absorption (TA), transient grating (TG), two-dimensional spectroscopy (2D)) in the visible domain andaccounts for anharmonic vibrations, sub-exponential relaxation and nonlinear electron-vibrational coupling. We subsequently applied the model for several case studies, such as carotenoid to bacteriochlorophyll excitation transfer in light-harvesting 2 complex (LH2) of purple bacteria, excitation transfer in perylene dyads or vibrational dynamics in hypericin. We have paid particular attention for detailed interpretation of lineshapes of 2D spectrograms employing, e.g. phase analysis and center line (CL) slopes with emphasis to study interplay of electronic, vibrational modulations, or finite excitation pulse durations.

The aim of the current work was to investigate the photo-induced charge transport at low temperatures, allowing more sensitive, detailed measurements of the first steps in the build-up of space charge fields, which modify the refractive index, leading to modern applications like volume holographic storage. We investigated the light-induced properties of SBN:Ce, KTO and KTN materials like origin of trapping centers which are involved in the charge transport process, characterization of trapping centers, like temperature dependence, illumination intensity dependence, evolution with time, spectral response, activation energies, the basic properties of the electronic excitations and photo-carriers localization based on results of absorption, light-induced absorption, photoluminescence, and photocurrent. The main contributions of this dissertation are summarized as follows: The experimental intensity dependence, temperature dependence, and decay process of the light-induced polaron (NIR) and VIS center absorption can be fitted with the help of a simplified charge transfer model (for SBN). The decay observed of the NIR polaron and the VIS centers is present due to the Fourier spectrometer light. The dissociation of the VIS centers into NIR centers under red light was observed. The model proposed for the VIS-centers in SBN is a triad structure related to the simultaneous bonding of two hole polarons and one electronic polaron.In KTN the emergence of the UV-light induced wide absorption bands in the NIR region with maxima at 0.69 0.8 eV at low temperatures is treated as a manifestation of the localization of photo-induced electrons and the formation of small electron polarons in close-neighbor Nb-Nb pair centers. Also, these properties in KTN can be fitted with the help of the simplified charge transfer model.

Cette thèse concerne l'ouverture de cycle des spiropyranes (SP) et leur utilisation comme interrupteurs contrôlés par impulsions laser. Nous avons élaboré un modèle théorique pour étudier cette réaction photochimique et développer des stratégies de contrôle.Les SP présentent des effets non adiabatiques impliquant un traitement quantique pour les électrons et les noyaux. L'approche multiconfigurationnelle dépendante du temps (MCTDH) est idéale car elle peut traiter des dynamiques quantiques impliquant plusieurs états électroniques. MCTDH a été appliqué avec succès aux calculs de spectres électroniques de systèmes montrant de forts effets non adiabatiques. Cependant, cette approche requiert au préalable les surfaces d'énergie potentielle (PES). Ces applications sont basées sur un modèle de couplage vibronique local de la PES à proximité du point de Franck-Condon (FC). Contrairement aux calculs de spectres de photoabsorbtion impliquant souvent de courtes échelles de temps et de faibles déformations autour du point de FC, la simulation de réactions photochimiques requiert une représentation adéquate des mouvements de large amplitude. Ce modèle doit donc être rendu plus flexible. Les modes normaux, utilisés dans le modèle standard, n'étant pas adaptés aux grandes déformations, nous avons choisi d'utiliser la méthode MCTDH en coordonnées curvilignes avec une reformulation systématique du modèle en coordonnées polysphériques afin d'obtenir une énergie cinétique nucléaire séparable.Même si le processus n'implique que l'état fondamental et le premier état excité, leurs configurations électroniques dominantes peuvent changer fortement le long de mouvements de grande amplitude. Nous avons donc développé une approche générale basée sur une étude systématique de quelques données ab initio pour générer le meilleur jeu d'états diabatiques d'un problème donné.De premières applications au benzopyrane (chromophore des SP) ont montré un bon accord avec l'expérience. / The focus of this thesis is the ring opening of spiropyrans (SP), and how these molecules can be used as photoswitches controlled with laser pulses. We have built a theoretical model to study this photochemical reaction and develop strategies for control.SP exhibit nonadiabatic effects, and therefore, their modelling requires a quantum description for both the electrons and the nuclei. The multiconfiguration time-dependent Hartree (MCTDH) approach is ideal in this case because it can treat quantum dynamics involving several electronic states. MCTDH was successfully applied to electronic spectra calculations of systems showing strong nonadiabatic effects. However, the corresponding potential energy surfaces (PES) for this approach are required first. These applications are based on a local vibronic coupling model of the PES in the neighbourhood of the Franck-Condon (FC) point.As opposed to calculating photoabsorption spectra that often involves short timescales and small deformations around the FC geometry, simulating photochemical reactions requires an adequate representation of large-amplitude motions. Thus, this model must be made more flexible.Normal modes, usually used for the standard model, are not adapted to large-amplitude deformations. We thus chose to run MCTDH in curvilinear coordinates and recast systematically the model in terms of polyspherical coordinates to produce a separable form for the nuclear kinetic energy.Even if only the ground and the first excited electronic states are involved in the process, their dominant electronic configurations may change significantly along large-amplitude motions. We have developed a general approach based on a systematic analysis of a few ab initio data to generate the best set of diabatic states for a given problem.Preliminary results applied to benzopyran (the chromophore of the SP) showed good agreement with the experiments.

L'avènement de la physique attoseconde a amené de nouveaux challenges tant expérimentaux que théoriques. En effet, l'observation de processus dynamiques, intervenant aux échelles de temps intrinsèques des mouvements des charges aux échelles atomiques, permet d'envisager des nouveaux processus pour lesquels le rôle des corrélations et des couplages non-adiabatiques deviennent primordiaux. Les travaux présentés dans ce manuscrit s'inscrivent dans le cadre de l'étude des molécules complexes, en particulier carbonées, soumises à une impulsion lumineuse courte. Pour de telles échelles de temps (femtoseconde / attoseconde) et d'énergie (IR / UVX), les principales approximations permettant l'étude des systèmes électroniques ne sont plus valides. Cette thèse présente les simulations théoriques réalisées permettant l'étude théorique de molécules dans de telles conditions. L'étude des dynamiques de migration de charges corrélées au sein des molécules de benzène, de différents hydrocarbures aromatiques polycycliques ainsi qu'au sein de molécules d'intérêt biologique telles que la phénylalanine, a été réalisée. Ce type de dynamiques n'a jamais pu être observé expérimentalement. Une attention particulière a donc été portée à la faisabilité d'une expérience dans le cas de la molécule de benzène. Les relaxations non-adiabatiques de la molécule de naphtalène soumise à une impulsion UVX ont été étudiées. Enfin, les dynamiques à l'échelle du cycle optique, rencontrées par un groupe de molécules de taille intermédiaire soumis à une impulsion IR, ont été abordées. Ces simulations ont permis d'interpréter des expériences pompe-sonde réalisées par des membres de notre équipe / The advent of attosecond physics has brought new experimental and theoretical challenges. Indeed, the observation of dynamic processes occurring at the intrinsic time scale of charge motion at atomic scale, allows to consider new processes for which the role of correlations and non-adiabatic couplings become primordial. The work presented in this manuscript falls in the context of the study of complex molecules subject to a short light pulse. For such time (femtosecond / attosecond) and energy scales (IR / XUV), the main approximations that permit the study of electronic systems are no longer appropriate. In this thesis, we present the simulations realized for the theoretical study of molecules in such conditions. We studied the correlated charge migration dynamics in several molecules like the benzene, different polycyclic aromatic hydrocarbons and molecules of biological interest such as phenylalanine. This kind of dynamics has never been observed experimentally. Hence, a particular attention was paid to the feasibility of an experiment in the case of the benzene molecule. The non-adiabatic relaxations of the naphthalene molecule subjected to a XUV pulse were also studied. Finally, dynamics occurring at the optical cycle time scale experienced by a group of medium-sized molecules subject to an IR pulse, were discussed. These simulations were used to interpret pump-probe experiments made by members of our team

<p>Quantum chemical computations provide convenient and effective ways for molecular design using computers. In this dissertation, the molecular designs of optimal nonlinear optical (NLO) materials were investigated through three aspects. First, an inverse molecular design method was developed using a linear combination of atomic potential approach based on a Hückel-like tight-binding framework, and the optimizations of NLO properties were shown to be both efficient and effective. Second, for molecules with large first-hyperpolarizabilities, a new donor-carbon-nanotube paradigm was proposed and analyzed. Third, frequency-dependent first-hyperpolarizabilities were predicted and interpreted based on experimental linear absorption spectra and Thomas-Kuhn sum rules. Finally, molecular interferometers were designed to control charge-transfer using vibrational excitation. In particular, an ab initio vibronic pathway analysis was developed to describe inelastic electron tunneling, and the mechanism of vibronic pathway interferences was explored.</p> / Dissertation

Orientador: René Alfonso Nome Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T09:25:13Z (GMT). No. of bitstreams: 1 Ferbonink_GuilhermeFerreira_M.pdf: 3339040 bytes, checksum: ef20418e159acb6b4683d177155e28be (MD5) Previous issue date: 2014 / Resumo: Nos últimos anos, várias descobertas vêm sendo realizada sobre como características intrínsecas de um dado sistema podem afetar a transferência eletrônica de energia. Um dos objetivos desta pesquisa é estudar experimentalmente como a estrutura vibrônica pode afetar a transferência eletrônica de energia em moléculas orgânicas segundo o modelo de Förster. Utilizando um sistema molecular com sobreposição espectral sobre bandas vibrônicas bem definidas, podemos verificar experimentalmente que o abaixamento da intensidade de emissão do doador unicamente nos comprimentos de onda de absorção do receptor caracteriza transferência de energia pelo modelo emissivo. Abaixamento da intensidade integrada de emissão caracteriza transferência de energia pelo mecanismo de Förster. A taxa de transferência de energia pelo mecanismo de Förster foi mais significativa quando a sobreposição espectral ocorre nas bandas vibrônica 0-1,0-2 ao invés da banda 0-0. Na segunda parte do trabalho realizado, aplicamos a técnica de absorção transiente para o estudo de nano prismas de ouro depositados sobre dois substratos diferentes. Neste trabalho, nós descrevemos a preparação e caracterização de matrizes isoladas de nanoprismas triangulares de ouro sobre o vidro contendo uma camada de ITO por litografia de nanoesferas. O espectro de absorção linear de Au / vidro e Au / ITO / vidro exibe ressonância de plásmon de superfície em 800 nm e 870 nm, com um deslocamento para o vermelho de 70 nm associado ao índice de refração de ITO. Foram realizadas medidas de espectroscopia de uma única cor de bombeio e prova com resolução temporal de 100 fs em comprimentos de onda inferiores a ressonância, em ressonância, e acima da ressonância de plásmon de superfície para cada um destes dois sistemas. A dinâmica ultra-rápida em ambos os sistemas pode ser bem descrita com um modelo que contabiliza o espalhamento elétron-elétron, o acoplamento elétron-fônon, e oscilações acústicas no término do resfriamento da estrutura de ouro. Os resultados para as nanopartículas de ouro, para cada um dos comprimentos de onda são bem descritos como tendo índice de refração complexo com dependência do comprimento de onda, que modula os sinais de bombeio e prova medidos / Abstract: Structure-property relationships for electronic energy transfer have been investigated in recent years. One of the goals of the present research is to perform an experimental study vibronic structure effects in electronic energy transfer between small organic molecules according to Forster¿s model. We have chosen organic molecules with well-defined spectral overlap between vibronic bands, which enabled us to experimentally characterize a decrease in donor emission intensity at the acceptor absorption wavelengths thereby indicating radiative energy transfer. A decrease in the emission integrated intensity characterizes energy transfer by the Forster mechanism. Forster energy transfer rates were higher when the spectral overlap involved 0-1 and 0-2 vibronic bands rather than 0-0 band. In the second part of this work, we have employed ultrafast transient absorption spectroscopy to investigated gold nano prisms deposited over two different substrates: Au over glass (Au/glass) and Au over ITO deposited on glass (Au/ITO/glass). In the present work, we describe the preparation and characterization of these two samples employing the nanosphere lithography technique. The linear absorption spectra of Au/glass and Au/ITO/glass respectively show surface plasmon resonances at 800 nm and 870 nm, with a 70nm redshift attributed to the ITO refractive index. We have performed femtosecond one-color pump-probe measurements with 100 fs time resolution below the surface plasmon resonance, at resonance, and above the surface plasmon resonance for each of these two systems. For both systems, the ultrafast dynamics can be well described with a model that takes into account electron-electron scattering, electron-phonon coupling, phonon-phonon coupling and acoustic damping. The wavelength-dependence observed can be explained in terms of the sample frequency-dependent complex refractive index which modulates the measured pump-probe signals / Mestrado / Físico-Química / Mestre em Química