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This thesis represents a quantum chemical treatise ofvarious types of interactions between radiation and molecularsystems, with special emphasis on the nonlinear opticalprocesses of Multi-Photon Absorption and Excited StateAbsorption. Excitation energies, transition dipole moments,two-photon and three-photon tensor elements have beencalculated from different approaches; density functional theoryandab-initiotheory, employing different orders ofcorrelation treatment with the purpose to provide accuratevalues as well as evaluate the quality of the lower ordermethods. A combined study of the Multi-Photon Absorption andExcited State Absorption processes is motivated partly becausethey both contribute to the total optical response of a systemsubjected to intense radiation, but also because of theirconnection through so-called sum-over-states expressions. Thelatter feature is exploited in a generalized few-states model,which incorporates the polarization of the light and thedirections of the transition dipole moments constructing anexcitation channel, which thereby enables a more comprehensivecomparison of the attained transition dipole moments withexperimental data. Moreover, by decomposing a complex nonlinearresponse process such as Two-Photon Absorption into moreintuitive quantities, generalized few-states models may alsoenable a more elaborate interpretation of computed orexperimental results from which guidelines can be extracted inorder to control or optimize the property of interest. Ageneral conclusion originating from these models is that thetransition dipole moments in an excitation channel should bealigned in order to maximize the Two-Photon Absorptionprobability. The computational framework employed is responsetheory which through the response functions (linear, quadratic,cubic) offers alternative routes for evaluating the propertiesin focus; either directly and untruncated through the singleresidue of the quadratic or cubic response func- tions orthrough various schemes of truncated sum-over-statesexpressions where the key ingredients, transition dipolemoments, can be identified from the single residue of thelinear response function and double residue of the quadraticresponse function. The range of systems treated in the thesisstretches from diatomics, such as carbon monoxide and lithiumhydride, via small to large fundamental organic molecules, suchas formaldehyde, tetrazine and the trans-polyenes, to largechro- mophores, such astrans-stilbene, cumulenes, dithienothiophene,paracyclophane and organo-metallic systems, such as theplatinum(II)ethynyl compounds. / QC 20120320

<p>This thesis represents a quantum chemical treatise ofvarious types of interactions between radiation and molecularsystems, with special emphasis on the nonlinear opticalprocesses of Multi-Photon Absorption and Excited StateAbsorption. Excitation energies, transition dipole moments,two-photon and three-photon tensor elements have beencalculated from different approaches; density functional theoryand<i>ab-initio</i>theory, employing different orders ofcorrelation treatment with the purpose to provide accuratevalues as well as evaluate the quality of the lower ordermethods. A combined study of the Multi-Photon Absorption andExcited State Absorption processes is motivated partly becausethey both contribute to the total optical response of a systemsubjected to intense radiation, but also because of theirconnection through so-called sum-over-states expressions. Thelatter feature is exploited in a generalized few-states model,which incorporates the polarization of the light and thedirections of the transition dipole moments constructing anexcitation channel, which thereby enables a more comprehensivecomparison of the attained transition dipole moments withexperimental data. Moreover, by decomposing a complex nonlinearresponse process such as Two-Photon Absorption into moreintuitive quantities, generalized few-states models may alsoenable a more elaborate interpretation of computed orexperimental results from which guidelines can be extracted inorder to control or optimize the property of interest. Ageneral conclusion originating from these models is that thetransition dipole moments in an excitation channel should bealigned in order to maximize the Two-Photon Absorptionprobability. The computational framework employed is responsetheory which through the response functions (linear, quadratic,cubic) offers alternative routes for evaluating the propertiesin focus; either directly and untruncated through the singleresidue of the quadratic or cubic response func- tions orthrough various schemes of truncated sum-over-statesexpressions where the key ingredients, transition dipolemoments, can be identified from the single residue of thelinear response function and double residue of the quadraticresponse function. The range of systems treated in the thesisstretches from diatomics, such as carbon monoxide and lithiumhydride, via small to large fundamental organic molecules, suchas formaldehyde, tetrazine and the trans-polyenes, to largechro- mophores, such as<i>trans</i>-stilbene, cumulenes, dithienothiophene,paracyclophane and organo-metallic systems, such as theplatinum(II)ethynyl compounds.</p>

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..

The experiments described in this thesis form an investigation into the path towards establishing the requirements of quantum computing in a linear optical system. Our qubits are polarisation encoded photons for which the basic operations of quantum computing, single qubit rotations, are a well understood problem. The difficulty lies in the interaction of photons. To achieve these we use measurement induced non-linearities. The first experiment in this thesis describes the thorough characterisation of a controlled-sign gate based on such non-linearities. The photons are provided as pairs generated through parametric down-conversion, and as such share correlations unlikely to carry over into large scale implementations of the future. En route to such larger circuits, a characterisation of the actions of the controlled-sign gate is conducted, when the input qubits have been generated independently from each other, revealing a large drop in process fidelity. To explore the cause of this degradation of the gate performance a thorough and highly accurate model of the gate is derived including the realistic description of faulty circuitry, photon loss and multi-photon emission by the source. By simulating the effects of the various noise sources individually, the heretofore largely ignored multi-photon emission is identified as the prime cause of the degraded gate performance, causing a drop in fidelity nearly three times as large as any other error source. I further draw the first comparison between the performance of an experimental gate to the error probabilities per gate derived as thresholds for fault-tolerant quantum computing. In the absence of a single vigourous threshold value, I compare the gate performance to the models that yielded the highest threshold to date as an upper bound and to the threshold of the Gremlin-model, which allows for the most general errors. Unsurprisingly this comparison reveals that the implemented gate is clearly insufficient, however just remedying the multi-photon emission error will allow this architecture to move to within striking distance of the boundary for fault-tolerant quantum computing. The utilised methodology can be applied to any gate in any architecture and can, combined with a suitable model of the noise sources, become an important guide for developments required to achieve fault tolerant quantum computing. The final experiment on the path towards linear optical quantum computing is the demonstration of a pair of basic versions of Shor's algorithm which display the essential entanglement for the algorithm. The results again highlight the need for extensive measurements to reveal the fundamental quality of the implemented algorithm, which is not accessible with limited indicative measurements. In the second part of the thesis, I describe two experiments on other forms of entanglement by extending the actions of a Fock-State filter, a filter that is capable of attenuating single photon states stronger than multi-photon states, to produce entangled states. Furthermore this device can be used in conjunction with standard wave-plates to extend the range of operations possible on the bi-photonic qutrit space, showing that this setup suffices to produce any desired qutrit state, thereby giving access to new measurement capabilities and in the process creating and proving the first entanglement between a qubit and a qutrit.

The experiments described in this thesis form an investigation into the path towards establishing the requirements of quantum computing in a linear optical system. Our qubits are polarisation encoded photons for which the basic operations of quantum computing, single qubit rotations, are a well understood problem. The difficulty lies in the interaction of photons. To achieve these we use measurement induced non-linearities. The first experiment in this thesis describes the thorough characterisation of a controlled-sign gate based on such non-linearities. The photons are provided as pairs generated through parametric down-conversion, and as such share correlations unlikely to carry over into large scale implementations of the future. En route to such larger circuits, a characterisation of the actions of the controlled-sign gate is conducted, when the input qubits have been generated independently from each other, revealing a large drop in process fidelity. To explore the cause of this degradation of the gate performance a thorough and highly accurate model of the gate is derived including the realistic description of faulty circuitry, photon loss and multi-photon emission by the source. By simulating the effects of the various noise sources individually, the heretofore largely ignored multi-photon emission is identified as the prime cause of the degraded gate performance, causing a drop in fidelity nearly three times as large as any other error source. I further draw the first comparison between the performance of an experimental gate to the error probabilities per gate derived as thresholds for fault-tolerant quantum computing. In the absence of a single vigourous threshold value, I compare the gate performance to the models that yielded the highest threshold to date as an upper bound and to the threshold of the Gremlin-model, which allows for the most general errors. Unsurprisingly this comparison reveals that the implemented gate is clearly insufficient, however just remedying the multi-photon emission error will allow this architecture to move to within striking distance of the boundary for fault-tolerant quantum computing. The utilised methodology can be applied to any gate in any architecture and can, combined with a suitable model of the noise sources, become an important guide for developments required to achieve fault tolerant quantum computing. The final experiment on the path towards linear optical quantum computing is the demonstration of a pair of basic versions of Shor's algorithm which display the essential entanglement for the algorithm. The results again highlight the need for extensive measurements to reveal the fundamental quality of the implemented algorithm, which is not accessible with limited indicative measurements. In the second part of the thesis, I describe two experiments on other forms of entanglement by extending the actions of a Fock-State filter, a filter that is capable of attenuating single photon states stronger than multi-photon states, to produce entangled states. Furthermore this device can be used in conjunction with standard wave-plates to extend the range of operations possible on the bi-photonic qutrit space, showing that this setup suffices to produce any desired qutrit state, thereby giving access to new measurement capabilities and in the process creating and proving the first entanglement between a qubit and a qutrit.

The experiments described in this thesis form an investigation into the path towards establishing the requirements of quantum computing in a linear optical system. Our qubits are polarisation encoded photons for which the basic operations of quantum computing, single qubit rotations, are a well understood problem. The difficulty lies in the interaction of photons. To achieve these we use measurement induced non-linearities. The first experiment in this thesis describes the thorough characterisation of a controlled-sign gate based on such non-linearities. The photons are provided as pairs generated through parametric down-conversion, and as such share correlations unlikely to carry over into large scale implementations of the future. En route to such larger circuits, a characterisation of the actions of the controlled-sign gate is conducted, when the input qubits have been generated independently from each other, revealing a large drop in process fidelity. To explore the cause of this degradation of the gate performance a thorough and highly accurate model of the gate is derived including the realistic description of faulty circuitry, photon loss and multi-photon emission by the source. By simulating the effects of the various noise sources individually, the heretofore largely ignored multi-photon emission is identified as the prime cause of the degraded gate performance, causing a drop in fidelity nearly three times as large as any other error source. I further draw the first comparison between the performance of an experimental gate to the error probabilities per gate derived as thresholds for fault-tolerant quantum computing. In the absence of a single vigourous threshold value, I compare the gate performance to the models that yielded the highest threshold to date as an upper bound and to the threshold of the Gremlin-model, which allows for the most general errors. Unsurprisingly this comparison reveals that the implemented gate is clearly insufficient, however just remedying the multi-photon emission error will allow this architecture to move to within striking distance of the boundary for fault-tolerant quantum computing. The utilised methodology can be applied to any gate in any architecture and can, combined with a suitable model of the noise sources, become an important guide for developments required to achieve fault tolerant quantum computing. The final experiment on the path towards linear optical quantum computing is the demonstration of a pair of basic versions of Shor's algorithm which display the essential entanglement for the algorithm. The results again highlight the need for extensive measurements to reveal the fundamental quality of the implemented algorithm, which is not accessible with limited indicative measurements. In the second part of the thesis, I describe two experiments on other forms of entanglement by extending the actions of a Fock-State filter, a filter that is capable of attenuating single photon states stronger than multi-photon states, to produce entangled states. Furthermore this device can be used in conjunction with standard wave-plates to extend the range of operations possible on the bi-photonic qutrit space, showing that this setup suffices to produce any desired qutrit state, thereby giving access to new measurement capabilities and in the process creating and proving the first entanglement between a qubit and a qutrit.

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No. of bitstreams: 1 leonardoaparecidodesouza.pdf: 3898214 bytes, checksum: c399d46a865d8df8a5d46b3a56175bfc (MD5) Previous issue date: 2011-03-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, métodos da mecânica quântica foram aplicados na investigação das propriedades estruturais e ópticas não-lineares (ONL) de moléculas de porfirina (P) e tetrafenilporfirina (TFP), além dos sistemas híbridos formados por diferentes derivados porfirínicos (ZnP, H2P, ZnP-pp e H2P-pp) adsorvidos sobre a superfície de um nanotubo de carbono de parede simples (SWNT) a(5,5). Todas as geometrias moleculares foram calculadas usando a Teoria do Funcional da Densidade (DFT) e a primeira hiperpolarizabilidade β foi calculada no nível Hartree-Fock (HF). Primeiramente, foram avaliados os aspectos estruturais de sessenta e quatro moléculas de porfirinas e tetrafenilporfirinas complexadas com Zn(II) (ZnP e ZnTFP) ou na forma protonada (H2P e H2TFP), modificadas por substituintes ligados diretamente ao anel macrociclotetrapirrólico. Menores distorções dos anéis de porfirinas e tetrafenilporfirinas foram encontradas quando havia o radical espaçador etinil (et) entre os grupos doador-receptor de elétrons, NH2 e NO2, respectivamente. A primeira hiperpolarizabilidade média para as moléculas foi calculada e valores de β mais intensificados foram encontrados para as porfirinas e tetrafenilporfirinas contendo ligantes do tipo push-pull, destacando-se aquelas que contêm em suas estruturas o grupo espaçador etinil. A segunda parte deste trabalho envolveu o estudo da estrutura, estabilidade e propriedade ONL de uma série de complexos porfirina-nanotubo (ZnPSWNT, H2P-SWNT, ZnP-pp-SWNT e H2P-pp-SWNT). Os resultados indicaram que a estabilidade dos complexos está diretamente relacionada com a presença do metal Zn(II), além disso, os grupos push-pull também contribuem para a estabilidade. A partir dos valores médios da energia de estabilização da série de isômeros, foi estabelecida a seguinte ordem de estabilidade: ZnP-pp-SWNT > ZnP-SWNT ~ H2P-pp-SWNT > H2PSWNT. A funcionalização dos nanotubos de carbono com porfirinas intensificam a propriedade ONL calculada. O valor de β aumenta significativamente quando o SWNT é funcionalizado com as moléculas de H2P-pp e ZnP-pp se comparado com as porfirinas livres. Os resultados obtidos nesta dissertação indicam que nanocompostos híbridos, tais como os representados por H2P-pp-SWNT e ZnP-pp-SWNT, podem representar uma importante alternativa na proposição de novos materiais de interesse que apresentam respostas ONL. / In this work, quantum mechanical methods were applied to investigate the structural and nonlinear optical (NLO) properties of porphyrin (P) and tetraphenylporphyrin (TFP) molecules, as well as hybrid systems formed by different porphyrin derivatives (ZnP, H2P, ZnP-pp and H2P-pp) adsorbed on the surface of a single-walled carbon nanotube (SWNT) a(5,5). The molecular geometries were calculated using Density Functional Theory (DFT) and the first hyperpolarizability was calculated at the Hartree-Fock (HF) level. Firstly, the structural aspects of sixty four porphyrin and tetraphenylporphyrin molecules complexed with Zn (II) (ZnP and ZnTFP) or in the protonated form (H2P and H2TFP), modified by substituents bound directly to the macrociclotetrapirrólico ring were evaluated. The smallest distortions of the porphyrin and tetraphenylporphyrin ring were found when the bridge group was the ethynyl radical (et) conecting the electron donor and acceptor groups, NH2 and NO2, respectively. The average first hyperpolarizability for these molecules was calculated and β values were larger for porphyrins and tetraphenylporphyrin containing push-pull ligands type, especially those that contain in their structures the ethynyl linker. The second part of this work involved the study of structure, stability and NLO property of a series of porphyrin-nanotube complex (ZnP-SWNT, H2P-SWNT, ZnP-pp-SWNT and H2P -pp-SWNT). The results indicated that the stability of the complexes is directly related to the presence of Zn(II) ion, in addition, the push-pull groups also contribute to the overall stability. By taking the average stabilization energy throughout the series of isomers, the following stability order was established: ZnP-pp-SWNT>ZnPSWNT~H2P-pp-SWNT>H2P-SWNT. The carbon nanotubes functionalization with porphyrins enhance the ONL response. The β values increase significantly when the SWNT is functionalized with the H2P-pp and ZnP-pp molecules if compared to the free porphyrins. The results obtained in this work indicate that hybrid nanocomposites, such as those represented by H2P-pp-SWNT and ZnP-pp-SWNT, might be an important alternative to the proposition of interesting new materials with ONL responses.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21585号 / 理博第4492号 / 新制||理||1645(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 谷村 吉隆, 教授 林 重彦, 教授 寺嶋 正秀 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM