Organic π-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structureactivity relationships useful for technological innovations. In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the iv efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchangecorrelation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different v semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations. In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1 † ) excitons, positive (P+ ) and negative (P- ) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particlehole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium. In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P + and Pis determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1 † ) mostly follows their lattice distortions. Geometry vi relaxation plays an important role in the localization of the S1 and T1 † excitons owing to the nonvariational construction of the excited state wavefunction. While, mean-field calculated P + , Pand T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and Pformation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LCwPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure. In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P + and Pexcitations in PPV and MEHPPV. We observe that the extent of self-trapping for P+ and Ppolarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work we present the results of L-asparagine H2O crystal growth and the study of their optical properties, linear and nonlinear, of crystal as grown and after being submitted to high doses of X-ray. Crystals were grown in aqueous solution by the method of slow evaporation of the solvent. Measurements optical absorption, Raman, thermal analysis and efficiency of second harmonic generation were carried out. The results demonstrate the good optical quality of the crystals for use in optical devices, comparable to that of KDP (KH2PO4). . / Neste trabalho apresentamos os resultados do crescimento de cristais de L-Asparagina-H2O e do estudo de suas propriedades ópticas, lineares e não lineares, do cristal como é crescido e após ser submetido a altas doses de raios-X. Os cristais foram crescidos em solução aquosa pelo método de evaporação lenta do solvente. Foram realizadas medidas de absorção óptica, Raman, análise térmica e eficiências de geração de segundo harmônico. Os resultados demonstram as boas qualidades ópticas dos cristais para aplicação em dispositivos ópticos, comparáveis ao do KDP (KH2PO4).

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi

<p>U&nbsp; disertaciji&nbsp; je&nbsp; sprovedeno&nbsp; teorijsko&nbsp; istraživanje&nbsp; fizičko-hemijskih&nbsp; svojstava&nbsp;elektronskog podsistema molekula sumanena. Proračuni su sprovedeni u okvirima DFT i TDDFT&nbsp; teorije&nbsp; sa&nbsp; B3LYP&nbsp; funkcionalom&nbsp; i&nbsp; 6-31Gd,&nbsp; 6-31Gdp i&nbsp; 6-31++Gdp&nbsp; bazisom.&nbsp; Za&nbsp; sve&nbsp;proračune&nbsp; u&nbsp; okvirima&nbsp; navedenog&nbsp; nivoa&nbsp; teorije,&nbsp; kori&scaron;ćen&nbsp; je&nbsp; softverski&nbsp; paket&nbsp; Gaussian03.&nbsp;Ispitana&nbsp; su:&nbsp; strukturna&nbsp; i&nbsp; optička&nbsp; (zajedno&nbsp; sa&nbsp; nelinearnim)&nbsp; svojstva&nbsp; sumanena&nbsp; i&nbsp; njegovih&nbsp;derivata dobijenih modifikovanjem sa atomima bora iazota, aromatična i inverziona svojstva&nbsp;svojstva&nbsp; sumanena&nbsp; i&nbsp; njegovih&nbsp; derivata,&nbsp; adsorpciona&nbsp; svojstva&nbsp; sumanena&nbsp; prema&nbsp; molekulima&nbsp;H₂, CO, CO_2&nbsp;i NH_3&nbsp;i uticaj spolja&scaron;njeg električnog polja na svojstva sumanena.</p><p>Prema&nbsp; dobijenim&nbsp; rezultatima,&nbsp; fundamentalna&nbsp; fizičko-hemijska&nbsp; svojstva&nbsp; molekula&nbsp;<br />sumanena mogu se efikasno i fino pode&scaron;avati supstitucijom i disupstitucijom hetero-atomima&nbsp;bora&nbsp; i&nbsp; azota.&nbsp; Dubina&nbsp; i&nbsp; inverziona&nbsp; barijera&nbsp; sumanena se&nbsp; na&nbsp; ovaj&nbsp; način&nbsp; može&nbsp; menjati&nbsp; u&nbsp; oba&nbsp;smera.&nbsp; Pokazalo&nbsp; se&nbsp; da&nbsp; su&nbsp; ova&nbsp; dva&nbsp; parametra&nbsp; u&nbsp; korelaciji,&nbsp; s&nbsp; obzirom&nbsp; da inverziona&nbsp; barijera&nbsp;skoro potpuno zavisi od dubine sumanena. Slično je i sa aromatičnim svojstvima prstenova,&nbsp;koja se u zavisnosti od broja uvedenih hetero-atomamenja od aromatične preko nearomatične&nbsp;do antiaromatične prirode. Optička svojstva su, pomenutim modifikacijama, takođe značajno&nbsp;pobolj&scaron;ana: apsorpcioni pikovi kod UV/Vis spektra se pomeraju ka vidljivoj oblasti, dok je&nbsp;hiperpolarizibilnost&nbsp; sumanena&nbsp; i&nbsp; derivata&nbsp; sa&nbsp; jednim&nbsp; atomom&nbsp; bora&nbsp; vi&scaron;a&nbsp; od&nbsp; referentnog&nbsp;molekula uree, respektivno, 9 i 49 puta.</p><p>Prema dobijenim rezultatima, adsorpciona svojstva sumanena su veoma kompetitivna&nbsp;sa&nbsp; ostalim&nbsp; organskim&nbsp; molekulima&nbsp; kao&nbsp; &scaron;to&nbsp; su&nbsp; ugljenične&nbsp; nanotube&nbsp; i&nbsp; fuleren&nbsp; C₆₀,&nbsp; usled&nbsp;postojanja&nbsp; značajnog&nbsp; dipolnog&nbsp; momenta&nbsp; zbog&nbsp; specifične&nbsp; geometrije.&nbsp; Posebno&nbsp; se&nbsp; ističu&nbsp;pozitivna adsorpciona svojstva prema molekulima H_2&nbsp;<br />i CO. Dok je prvo pomenuti bitan sa&nbsp;energetskog&nbsp; aspekta,&nbsp; specifičnost&nbsp; drugog&nbsp; molekula&nbsp; se&nbsp; ogleda&nbsp; u&nbsp; činjenici&nbsp; da&nbsp; ne&nbsp; može&nbsp; biti&nbsp;adsorbovan od strane ugljeničnih nanotuba.&nbsp;</p><p>Potencijal sumanena, posebno u oblasti organske elektronike, dodatno ističu i rezultati&nbsp;ispitivanja&nbsp; uticaja&nbsp; spolja&scaron;njeg&nbsp; električnog&nbsp; polja.&nbsp; Naime,&nbsp; dobijeni&nbsp; rezultati&nbsp; ukazuju&nbsp; da&nbsp; se&nbsp;specifična&nbsp; (posebno&nbsp; adsorpciona)&nbsp; svojstva&nbsp; sumanena&nbsp; mogu&nbsp; dodatno&nbsp; pobolj&scaron;ati&nbsp; primenom&nbsp;slabog, i eksperimentalno lako ostvarljivog, električnog &nbsp;polja, jer se intenzivira razdvajanje&nbsp;naelektrisanja.</p> / <p>Theoretical&nbsp; investigation&nbsp; of&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; electron&nbsp; subsystem&nbsp; of&nbsp;sumanene&nbsp; molecule&nbsp; has&nbsp; been&nbsp; conducted&nbsp; in&nbsp; this&nbsp; doctoral&nbsp; work.&nbsp; Calculations &nbsp;are&nbsp; performed&nbsp;within DFT and TD-DFT with B3LYP functional and 6-31Gd, 6-31Gdp i &nbsp; 6-31++Gdp basis&nbsp;sets. For all calculations, on the mentioned level of theory, Gaussian03software package was&nbsp;used.&nbsp; Investigation&nbsp; encompassed:&nbsp; structural &nbsp; and&nbsp; optical&nbsp; (including&nbsp; nonlinear)&nbsp; properties&nbsp; of&nbsp;sumanene&nbsp; and&nbsp; its&nbsp; derivatives&nbsp; obtained&nbsp; by&nbsp; modification&nbsp; with&nbsp; boron&nbsp; and&nbsp; nitrogen&nbsp; atoms,&nbsp;aromatic and bowl to bowl inversion properties of sumanene and its derivatives, adsorption&nbsp;properties of sumanene towards H₂, CO, CO_2&nbsp;i NH_3&nbsp;molecules and the influence of external&nbsp;electric field to the properties of sumanene.</p><p>According to obtained results, fundamental physicochemical properties of sumanene&nbsp;molecule could be efficiently and finely adjusted with the monosubstitution and disubstitution&nbsp;with&nbsp; hetero-atoms&nbsp; of&nbsp; boron&nbsp; and&nbsp; nitrogen.&nbsp; Bowl&nbsp; depth and&nbsp; bowl&nbsp; to&nbsp; bowl&nbsp; inversion&nbsp; barrier&nbsp;could&nbsp; be&nbsp; tuned&nbsp; in&nbsp; both&nbsp; directions.&nbsp; It&nbsp; was&nbsp; demonstrated&nbsp; that&nbsp; these&nbsp; two&nbsp; parameters&nbsp; are&nbsp;correlated, since bowl to bowl inversion barrier principally depends on the fourth power of&nbsp;bowl&nbsp; depth.&nbsp; Similar&nbsp; situation&nbsp; is&nbsp; with&nbsp; aromatic&nbsp; nature&nbsp; of&nbsp; sumanene&nbsp; rings,&nbsp; which&nbsp; change,&nbsp;depending&nbsp; on&nbsp; the&nbsp; number&nbsp; of&nbsp; introduced&nbsp; boron&nbsp; and&nbsp; nitrogen&nbsp; atoms,&nbsp; from&nbsp; aromatic&nbsp; through&nbsp;non-aromatic&nbsp; towards&nbsp; anti-aromatic&nbsp; nature.&nbsp; Thanks&nbsp; to&nbsp; mentioned&nbsp; modifications,&nbsp; optical&nbsp;properties&nbsp; are&nbsp; improved&nbsp; as&nbsp; well:&nbsp; absorption&nbsp; peaks&nbsp; in&nbsp; UV/Vis&nbsp; spectra&nbsp; shift&nbsp; towards&nbsp; visible&nbsp;area,&nbsp; while&nbsp; hyperpolarizabilities&nbsp; of&nbsp; sumanene&nbsp; and&nbsp; its&nbsp; derivative&nbsp; containing&nbsp; one&nbsp; boron&nbsp; atom&nbsp;are higher than hyperpolarizability of referent molecule of urea, respectively, 9 and 49 times.&nbsp;</p><p>Thanks&nbsp; to&nbsp; significant&nbsp; dipole&nbsp; moment&nbsp; due&nbsp; to&nbsp; the&nbsp; specific&nbsp; geometry, &nbsp;nvestigated &nbsp;adsorption properties of sumanene are very competitive to the other &nbsp;organic molecules such&nbsp;as carbon nanotubes and fullerene C₆₀. Positive adsorption properties of sumanene towards H_2&nbsp;and CO molecules are distinguished. While the H_2&nbsp;molecule is important from the energetic&nbsp;aspects, specificity of CO molecules is that it can&rsquo;t be adsorbed by carbon nanotubes.</p><p>Potential&nbsp; of&nbsp; sumanene,&nbsp; especially&nbsp; in&nbsp; the&nbsp; field&nbsp; of&nbsp; organic&nbsp; electronics,&nbsp; is &nbsp;emphasized&nbsp;through the obtained results related to the investigation of the influence of external electric&nbsp;field.&nbsp; Obtained&nbsp; results&nbsp; indicate&nbsp; that&nbsp; specific&nbsp; (especially&nbsp; adsorption)&nbsp; properties&nbsp; of&nbsp; sumanene&nbsp;could be additionally improved by application of &nbsp;weak, and experimentally easily achievable,&nbsp;external electric field, due to the higher charge separation.&nbsp;</p>

No description available.

El coneixement de la superfície d'energia potencial (PES) ha estat essencial en el món de la química teòrica per tal de discutir tant la reactivitat química com l'estructura i l'espectroscòpia molecular. En el camp de la reactivitat química es hem proposat continuar amb el desenvolupament de nova metodologia dins el marc de la teoria del funcional de la densitat conceptual. En particular aquesta tesis es centrarà en els següents punts:a) El nombre i la naturalesa dels seus punts estacionaris del PES poden sofrir canvis radicals modificant el nivell de càlcul utilitzats, de tal manera que per estar segurs de la seva naturalesa cal anar a nivells de càlcul molt elevats. La duresa és una mesura de la resistència d'un sistema químic a canviar la seva configuració electrònica, i segons el principi de màxima duresa on hi hagi un mínim o un màxim d'energia trobarem un màxim o un mínim de duresa, respectivament. A l'escollir tot un conjunt de reaccions problemàtiques des del punt de vista de presència de punts estacionaris erronis, hem observat que els perfils de duresa són més independents de la base i del mètode utilitzats, a més a més sempre presenten el perfil correcte. b) Hem desenvolupat noves expressions basades en les integracions dels kernels de duresa per tal de determinar la duresa global d'una molècula de manera més precisa que la utilitzada habitualment que està basada en el càlcul numèric de la derivada segona de l'energia respecte al número d'electrons.c) Hem estudiat la validesa del principis de màxima duresa i de mínima polaritzabiliat en les vibracions asimètriques en sistemes aromàtics. Hem trobat que per aquests sistemes alguns modes vibracionals incompleixen aquests principis i hem analitzat la relació d'aquest l'incompliment amb l'efecte de l'acoblament pseudo-Jahn-Teller. A més a més, hem postulat tot un conjunt de regles molt senzilles que ens permetien deduir si una molècula compliria o no aquests principis sense la realització de cap càlcul previ. Tota aquesta informació ha estat essencial per poder determinar exactament quines són les causes del compliment o l'incompliment del MHP i MPP.d) Finalment, hem realitzat una expansió de l'energia funcional en termes del nombre d'electrons i de les coordenades normals dintre del conjunt canònic. En la comparació d'aquesta expansió amb l'expansió de l'energia del nombre d'electrons i del potencial extern hem pogut recuperar d'una altra forma diferent tot un conjunt de relacions ja conegudes entre alguns coneguts descriptors de reactivitat del funcional de la densitat i en poden establir tot un conjunt de noves relacions i de nous descriptors.Dins del marc de les propietats moleculars es proposa generalitzar i millorar la metodologia pel càlcul de la contribució vibracional (Pvib) a les propietats òptiques no lineals (NLO). Tot i que la Pvib no s'ha tingut en compte en la majoria dels estudis teòrics publicats de les propietats NLO, recentment s'ha comprovat que la Pvib de diversos polímers orgànics amb altes propietats òptiques no lineals és fins i tot més gran que la contribució electrònica. Per tant, tenir en compte la Pvib és essencial en el disseny dels nous materials òptics no lineals utilitzats en el camp de la informàtica, les telecomunicacions i la tecnologia làser. Les principals línies d'aquesta tesis sobre aquest tema són:a) Hem calculat per primera vegada els termes d'alt ordre de Pvib de diversos polímers orgànics amb l'objectiu d'avaluar la seva importància i la convergència de les sèries de Taylor que defineixen aquestes contribucions vibracionals.b) Hem avaluat les contribucions electròniques i vibracionals per una sèrie de molècules orgàniques representatives utilitzant diferents metodologies, per tal de poder de determinar quina és la manera més senzilla per poder calcular les propietats NLO amb una precisió semiquantitativa. / The knowledge of the potential energy surface (PES) has been essential in the world of the theoretical chemistry to discuss such as the chemistry reactivity as the molecular spectroscopy. In the reactivity chemistry we are interested to develop new methodology in the field of the conceptual functional density theory. This thesis will be center in the following points:a) The number and character of the different stationary points of the PES can have radical changes modifying the calculation level used. This fact produces that to be sure of the character of a stationary point is necessary to arrive a very precise calculation level. The hardness is a measure of the resistance of a chemistry system to change his electronic configuration, and taking into account the maximum hardness principle, where there is a minimum or a maximum of energy, there also is a minimum or a maximum of hardness, respectively. Choosing a set of problematic reactions in the number of stationary points, we noted that the hardness is more independent of the base and the method used and it always shows the correct shape.b) We made new expressions based in the integrations of the hardness kernel to predict the global hardness of a molecule in a more precise way that the numerical second derivative of the energy respect to the number of electrons.c) We studied the validity of the maximum hardness and the minimum polarizability principles in the asymmetric vibrations in aromatic systems. We found that for theses systems some vibrational modes break these principles and we studied the relationship of this non-fulfillment with the pseudo-Jahn-Teller effect. Moreover, we postulated a set of simple rules, that allows deducing if a molecule will follow or not these rules without a previous calculation. All this information has been essential to exactly determine the reasons of the fulfillment or non-fulfillment of the MHP and MPP.d) Finally, we made an expansion of the functional energy respect to the number of electrons and the normal coordinates into the canonic ensemble. The comparison of this expansion with the expansion of the energy respect to the number of electrons and the external potential give the recuperation of some know relations between traditional reactivity descriptors of DFT, but a different way, and establish a set of new relations and descriptors.In the field of molecular properties we propose to generalize and improve the methodology to calculate the vibrational contribution (Pvib) to the non-linear optical properties (NLO). Despite of that the Pvib is not taking account into the majority of the theoretical studies published of the properties NLO, it has recently been checked that the Pvib of different organic molecules with high NLO properties is bigger that the electronic contribution. Thus, the Pvib is essential to pattern new NLO materials used in informatics, telecommunications, and laser technology. The main lines of the research about this subject are:a) We have calculated for the first time the high terms of the Pvib for different organic polymer with the goal to evaluate the importance and the convergence of the Taylor series that define the vibrational contributions.b) We have evaluated the electronic and vibrational contributions for different representative organic molecules using different methodologies to predict the cheaper way to calculate the NLO properties with semi quantitative precision.

Les formats de modulation bidimensionnels (i.e. basés sur l’amplitude et la phase de l’onde porteuse) ont gagné depuis peu le domaine des transmissions par fibre optique grâce aux progrès conjoints de l’électronique rapide et du traitement du signal, indispensables pour réaliser les récepteurs opto-électroniques utilisant la détection cohérente des signaux optiques. Pour pallier les limites actuelles en rapidité de commutation des circuits intégrés électroniques, une voie de recherche a été ouverte il y a quelques années, consistant à utiliser des technologies optiques pour faciliter la parallélisation du traitement du signal, notamment dans l’étape d’échantillonnage ultra-rapide du signal rendu possible par des horloges optiques très performantes. Le thème principal de cette thèse concerne l’étude théorique et expérimentale de la fonction de conversion analogique-numérique (ADC) de signaux optiques par un récepteur opto-électronique cohérent, associant les étapes d’échantillonnage optique linéaire, de conversion analogique-numérique et de traitement du signal. Un prototype, utilisant une solution originale pour la source d’échantillonnage, est modélisé, réalisé et caractérisé, permettant la reconstruction temporelle de signaux optiques modulés selon divers formats : NRZ, QPSK, 16-QAM. Les limitations optiques et électroniques du système sont analysées, notamment l’impact sur la reconstruction des signaux de divers paramètres : le taux d’extinction de la source optique, les paramètres de l’ADC (bande passante BW, temps d’intégration et nombre effectif de bits ENOB). Par ailleurs, de nouveaux algorithmes de traitement du signal sont proposés dans le cadre de la transmission optique cohérente à haut débit utilisant des formats de modulation bidimensionnels (amplitude et phase) : deux solutions sont proposées pour la compensation du déséquilibre de quadrature IQ dans les transmissions mono-porteuses: une méthode originale de l’estimation du maximum du rapport signal sur bruit ainsi qu’une nouvelle structure de compensation et d’égalisation conjointes; ces deux méthodes sont validées expérimentalement et numériquement avec un signal 16-QAM. Par ailleurs, une solution améliorée de récupération de porteuse (décalage de fréquence et estimation de la phase), basée sur une décomposition harmonique circulaire de la fonction de maximum de vraisemblance logarithmique, est validée numériquement pour la première fois dans le contexte des transmissions optiques (jusqu’à une modulation de 128-QAM). Enfin les outils développés dans ce travail ont finalement permis la démonstration d’une transmission sur 100 km d’un signal QPSK à 10 Gbaud fortement limité par un bruit de phase non linéaire et régénéré optiquement à l’aide d’un limiteur de puissance préservant la phase basé sur une nanocavité de cristal photonique. / Bi-dimensional modulation formats based on amplitude and phase signal modulation, are now commonly used in optical communications thanks to breakthroughs in the field of electronic and digital signal processing (DSP) required in coherent optical receivers. Photonic solutions could compensate for nowadays limitations of electrical circuits bandwidth by facilitating the signal processing parallelization. Photonic is particularly interesting for signal sampling thanks to available stable optical clocks. The heart of the present work concerns analog-to-digital conversion (ADC) as a key element in coherent detection. A prototype of linear optical sampling using an original solution for the optical sampling source, is built and validated with the successful equivalent time reconstruction of NRZ, QPSK and 16-QAM signals. Some optical and electrical limitations of the system are experimentally and numerically analyzed, notably the extinction ratio of the optical source or the ADC parameters (bandwidth, integration time, effective number of bits ENOB). Moreover, some new DSPs tools are developed for optical transmission using bi-dimensional modulation formats (amplitude and phase). Two solutions are proposed for IQ quadrature imbalance compensation in single carrier optical coherent transmission: an original method of maximum signal-to-noise ratio estimation (MSEM) and a new structure for joint compensation and equalization; these methods are experimentally and numerically validated with 16-QAM signals. Moreover, an improved solution for carrier recovery (frequency offset and phase estimation) based on a circular harmonic expansion of a maximum loglikelihood function is studied for the first time in the context of optical telecommunications. This solution which can operate with any kind of bi-dimensional modulation format signal is numerically validated up to 128-QAM. All the DSP tools developed in this work are finally used in a demonstration of a 10 Gbaud QPSK 100 km transmission experiment, featuring a strong non-linear phase noise limitation and regenerated using a phase preserving and power limiting function based on a photonic crystal nanocavity.