Ο όρος μη-γραμμική οπτική αντιπροσωπεύει τον κλάδο της οπτικής ο οποίος μελετά την αλληλεπίδραση της ύλης με ακτινοβολία πολύ ισχυρής έντασης. Όταν ένα υλικό εκτεθεί σε ακτινοβολία υψηλής έντασης όπως αυτή του laser, οι οπτικές του ιδιότητες αλλάζουν εξαιτίας της πόλωσης που επάγεται στα δομικά υλικά του και το αποτέλεσμα είναι η αλλαγή των οπτικών του ιδιοτήτων. Αυτό με τη σειρά του οδηγεί σε μια πληθώρα φαινομένων τα οποία μας βοηθούν στη κατανόηση της δομής του υλικού αλλά και των φυσικών μηχανισμών που κρύβονται πίσω από αυτά. Στην παρούσα μεταπτυχιακή εργασία μελετώνται οι μη γραμμικές οπτικές ιδιότητες χρωμοφόρων τύπου BODIPY υπό μορφή διαλυμάτων. Η σύνθεση των μορίων έγινε στο Ινστιτούτο Φυσικοχημείας του ΕΚΕΦΕ ΔΗΜΟΚΡΙΤΟΣ από την ερευνητική ομάδα του κ.Πιστόλη στα πλαίσια ενός έργου ΘΑΛΛΗ. Η διάρθωση της εργασίας είναι η εξής: Στο πρώτο κεφάλαιο γίνεται μια εισαγωγή και παρουσιάζονται κάποιες βασικές έννοιες της μη γραμμικής οπτικής. Ενώ ταυτόχρονα αναπτύσσονται αναλυτικότερα μερικά φαινόμενα τα οποία οφείλονται στη μη γραμμική επιδεκτικότητα τρίτης τάξης. Στο δεύτερο κεφάλαιο γίνεται η παρουσίαση της πειραματικής τεχνικής Z-scan, που χρησιμοποιήθηκε για τη διεξαγωγή των πειραμάτων, αλλά και η διαδικασία που ακολουθήθηκε για την εξαγωγή των μη γραμμικών οπτικών ιδιοτήτων από τα πειραματικά δεδομένα. Στο τρίτο κεφάλαιο παρουσιάζονται τα πειραματικά αποτελέσματα των συστημάτων που μελετήθηκαν. Αρχικά, παρουσιάζεται μια περιγραφή των ιδιαίτερων φωτοφυσικών ιδιοτήτων των μορίων BODIPY που μελετήθηκαν. 'Επειτα, ακολουθεί η μη γραμμική οπτική απόκριση των συστημάτων για διέγερση στα 532nm και 1064nm με παλμούς χρονικής διάρκειας 532ps και 4ns. Τέλος, ακολουθούν τα συμπεράσματα από τη μελέτη των συστημάτων και μια πρόταση για μελλοντική μελέτη. / Nonlinear optics (NLO) is related to laser-matter interactions, as well as the changes which are induced in materials during their interaction with intense laser fields. Laser beams can provide strong enough electromagnetic fields, capable of inducing optical changes. In these cases the response of the material is not linearly dependent on the intensity of the electric field. The primary objective of this thesis was the investigation of the non-linear optical properties of BODIPY derivatives. In particular, we focused on the determination of the second-order hyperpolarizability in order to correlate the magnitude and the sign of the observed nonlinearities with their photophysical characteristics. The main experimental technique used was the Z-scan technique, employing 35 ps and 4 ns laser pulses at both 532 nm and 1064 nm. The molecules were synthesized by the research group of Dr. Pistolis at the Institute of Physical Chemistry NCSR ''Demokritos" as a part of the ''THALIS" programme. The structure of the thesis is as follows: In Chapter 1, the basic NLO phenomena and the corresponding related nonlinear optical parameters are introduced. In Chapter 2, the theoretical background of the Z-scan technique is briefly presented, while the Z-scan experimental set-up is fully described. In Chapter 3, experimental results on the NLO properties of the Bodipy derivatives are presented. The relationship between the nonlinear optical properties and photophysical properties of the derivatives is also considered. The conclusion summarizes the results of the NLO response of the BODIPY derivatives and details a proposal for future work..

Depuis plusieurs années, le laboratoire SPCTS de Limoges a focalisé son attention sur l’étude des matériaux tellurates (à base de cations Te6+), dont les propriétés optiques non-linéaires du troisième ordre (χ(3)) doivent être encore supérieures à celles des matériaux tellurites (à base de cations Te4+) traditionnellement considérés. En effet, les calculs ab initio montrent que les propriétés non-linéaires d’ordre trois du composé tellurate TeO3-β sont environ 10 fois plus élevées que celles du composé tellurite TeO2-α. A ce titre, une étude théorique du système (1-x)TeO2+ xTeO3 a été entreprise afin de comprendre l’origine structurale de cette importante différence de propriétés. Les résultats de cette étude ont montré que cette différence était liée à l’augmentation du « degré de polymérisation » et à la diminution du gap énergétique associées à chacune des phases de ce système et ce, avec le taux croissant en cations Te6+. Ces conclusions ont ensuite été généralisées à travers une étude plus globale menée sur un grand nombre de composés oxydes de type MnOm et MnTepOm. Une attention particulière a été portée aux propriétés non-linéaires du composé TeO3-β. Une étude expérimentale puis théorique a permis de mettre en évidence que ses exceptionnelles propriétés non-linéaires étaient directement corrélées aux propriétés des liaisons chimiques le constituant. Compte tenu de l’ensemble de ces résultats, la synthèse de verres tellurates a été envisagée à travers l’étude du système TeO2-Mg3TeO6. Outre leurs forts intérêts pour l’optique, les matériaux tellurates sont aussi de bons candidats en vue d’une intégration dans des dispositifs de type « Low Temperature Cofired Ceramics ». C’est pourquoi, l’étude du composé Bi6Te2O15 a été entreprise. A cet égard, son protocole de frittage a été optimisé au moyen de la technologie « Spark Plasma Sintering » (SPS), et ses propriétés diélectriques mesurées se sont révélées prometteuses. / For several years, SPCTS laboratory of Limoges has focalized his attention to the study of tellurate materials (Te6+ cations-based compounds), whose third order non-linear optical properties (χ(3)) must be superior to those of tellurite materials (Te4+ cations-based compounds) traditionally considered. Indeed, ab initio calculations show those the third order non-linear optical properties of the TeO3-β tellurate compound are about 10 time higher than that of TeO2-α tellurite phase. In this connection, the theoretical study of the (1-x)TeO2+ xTeO3 system was undertaken in order to understand the structural origins of these properties. Results have shown that the increasing of the “polymerization degree” and the decreasing of the energetical gap associated to each structure of this system, with the increasing ratio of Te6+ cations were at the origin of this change of properties. These conclusions were generalized through the study of many oxide compounds such as MnOm and MnTepOm. A special attention was paid to the non-linear properties of the TeO3-β compound. Experimental and theoretical studies allowed highlighting that its exceptional properties were correlated to its chemical bonding properties. Taking into account all these results, the synthesis of tellurate glasses was investigated, through the study of the TeO2-Mg3TeO6 binary system. Besides their great interest for optical applications, tellurate materials are also good candidates for LTCC applications. Therefore the study of the Bi6Te2O15 compound was also managed in this work. Its sintering process was optimized using the “Spark Plasma Sintering” technology, and its dielectric properties measurements have evidenced very promising values.

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).

<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.