The main theme of this thesis is to study effects of different environments on geometric and electronic structures, as well as optical responses, of molecules using time-(in)dependent density functional theory. Theoretical calculations have been carried out for properties that can be measured by conventional and advanced experimental techniques, including one-photon absorption (OPA), two-photon absorption (TPA), surface-enhanced Raman scattering (SERS) and second order nonlinear optical (NLO) response. The obtained good agreement between the theory and the experiment allows to further extract useful information about inter- and intra-molecular interactions that are not accessible experimentally. By comparing calculated one-photon absorption spectra of aluminum phthalocyanine chloride (AlPcCl) and AlPcCl -water complexes with the corresponding experiments, detailed information about the interaction between water molecules and AlPcCl, and geometric changes of AlPcCl molecule has been obtained. Effects of aggregation on two-photon absorption spectra of octupolar molecules have been examined. It is shown that the formation of clusters through inter-molecular hydrogen bonding can drastically change profiles of TPA spectra. It has also demonstrated that a well designed molecular aggregate/cluster, dendrimer, can enhance the second order nonlinear optical response of the molecules. In collaboration with experimentalists, a series of end-capped triply branched dendritic chromophores have been characterized, which can lead to large enhancement of the second order NLO property when the dipoles of the three branches in the dendrimers are highly parallelized. Surface-enhanced Raman scattering has made the detection of single molecules on metal surface become possible. Chemically bonded molecule-metal systems have been extensively studied. We have shown in a joint experimental and theoretical work that stable Raman spectra of a non-bonding molecule, perylene, physically adsorbed on Ag nano-particles can also be observed at low temperature. It is found that the local enhanced field has a tendency to drive molecule toward a gap of two closely lying nano-particles. The trapped molecule can thus provide a stable Raman spectrum with high resolution when its thermal motion is reduced at low temperature. For the ever growing size of molecular complexes, there is always the need to develop new computational methods. A conceptually simple but computationally efficient method, named as central insertion scheme (CIS), is proposed that allows to calculate electronic structure of quasi-periodic system containing more than 100,000 electrons at density functional theory levels. It enables to monitor the evolution of electronic structure with respect to the size of the system. / QC 20100823

Inter-molecular interactions have significant influences on linear and nonlinear optical properties of molecules including one- and two-photon absorptions, emissions, and various high order nonlinear polarizations. The related investigation has become an active and challenging research area. The theoretical structure-to-property relationship obtained from quantum chemical calculations of single organic conjugated molecules often can not be directly applied to real materials in condensed phases. One has to consider the effect of environment, that is, inter-molecular interactions, where the model systems experience in real experiments or applications. The change of molecular conformations under all kinds of interactions and its effects on linear and nonlinear optical properties are the central issue of this thesis. Special attentions have been paid to symmetrical diamino substituted distyrylbenzene chromophores with different torsional angles, two dipolar merocyanine dyes of various orientations, two isomers of a V-shaped 2-hydroxypyrimidine derivative and their various dimers, and the structural fluctuations of interacting polar chromophores in solutions. Quantum chemical methods in combination with molecular dynamics simulations have been employed to study molecular conformations and optical properties in solutions, in particular the solvent and aggregation effects on one- and two-photon absorption. More specifically, time-dependent density functional theory has been used for all electronic calculations, while the polarizable continuum model and supermolecule approach have also been employed to take into account solvent effects. Moreover, the propagation of an ultrashort laser pulse through a one-dimensional asymmetric organic molecular medium which possesses large permanent dipole moments has been simulated by solving full Maxwell-Bloch equations using predictor-corrector finite-difference time-domain method. We have focused on the supercontinuum generation of spectra and the formation of attosecond pulses. / QC20100630

Structure-property relationships for two-photon absorption (2PA) in branched organic chromophores is a topic of current interest, as is the design of chromophores with advantageous properties for two-photon laser scanning microscopy (2PLSM). The main goals of this dissertation were to study and explain the one-photon absorption (1PA) and 2PA properties of cruciform chromophores based on 1,4-distyryl-2,5-bis(phenylethynyl)benzene with varying electron donor (D) and acceptor (A) groups, and to characterize the 2PLSM-relevant response of some of these chromophores and a set of dipolar chromophores to binding with zinc ions. The compounds were studied by 1PA, fluorescence and 2PA spectroscopy. A ππ* exciton model was developed to explain the spectral properties of the 1,4-distyryl-2,5-bis(phenylethynyl)benzene cruciform with no D or A groups or with four identical D groups at the termini of the linear arms of the chromophore. This model indicated that there is some coupling and mixing of the lowest excited states e of the linear arms, leading to splitting of the 1PA spectrum of the cruciform. There was little coupling or mixing of the higher excited states e′ accessed in 2PA, leading to a two-band 2PA spectrum for the chromophore, in contrast to cruciform compounds in the literature with identical conjugated arms, which have one visible 2PA band. For cruciforms with D groups on the styryl arm and A character on the terminal phenyls of the phenylethynyl arms (D/A cruciforms), the ππ* exciton model was complemented with a charge-transfer (CT) exciton model describing interactions of charge-transfer pathways between the D and A groups. This model explained the broadness of the 1PA band of D/A cruciforms as well as the two 2PA bands observed for these chromophores. The fluorescence and 2PA spectral responses to binding of Zn²⁺ ions to the D or A groups of some cruciform compounds were also assessed, to provide insight into the design of new analyte-sensing cruciforms for 2PLSM that take advantage of enhancement or reduction of D/A character upon analyte binding. It was found that canceling charge donation from the D groups in differing D/A cruciforms resulted in fluorescence and 2PA spectra nearly indistinguishable from each other, suggesting that turn-off of D groups is not an optimal modality of 2PLSM analyte sensing in cruciforms. Binding Zn²⁺ to A groups was shown to result in an increase in the D/A character of the cruciform, with fluorescence peak energies that changed depending on the location of the A group. It is suggested that the use of non-binding donors and analyte-binding A groups in differing patterns on the arms could be a valuable design motif to achieve 2PLSM sensor compounds based on this cruciform structure. The 2PA spectra of a set of dipolar Zn²⁺ sensing dyes designed for ratiometric imaging in 2PLSM were also studied. These dyes had moderate 2PA strength, with redshifts of fluorescence 2PA spectra on Zn²⁺ binding. The isosbestic point of 2PA of most chromophores was within the range of 2PLSM excitation sources commonly used, rendering these dyes good candidates for use in ratiometric sensing in 2PLSM.

Στην εργασία αυτή θα ασχοληθούμε με τη διφωτονική απορρόφηση και τις εφαρμογές της. Θα πρέπει πρώτα να πούμε δύο λόγια γι’αυτήν, να εξηγήσουμε περί τίνος πρόκειται και γι’αυτό θα αρχίσουμε από τα βασικά. Όταν ηλεκτρομαγνητική ακτινοβολία κυκλικής συχνότητας ω0 προσπίπτει σε ένα υλικό μέσο, τα άτομά του λειτουργούν σαν ταλαντωτές, με την έννοια πως ταλαντώνονται στη συχνότητα της ακτινοβολίας, απορροφώντας την και επανεκπέμποντάς την. Παρομοιάζοντας έναν τέτοιο ταλαντωτή με σύστημα μάζας-ελατηρίου, το ρόλο της μάζας τον παίζει το ηλεκτρόνιο (για λόγους απλότητας θεωρούμε πως το άτομο έχει μόνο ένα) και το ρόλο του ελατηρίου οι δυνάμεις έλξης ηλεκτρονίου-πυρήνα. Το «ελατήριο» στη μιά του άκρη είναι στερεωμένο στον πυρήνα, που λόγο μεγάλης μάζας (σε σύγκριση με το ηλεκτρόνιο) θεωρείται ακίνητος. Όταν η ένταση του Η/Μ πεδίου είναι μικρή, το ηλεκτρόνιο δεν απομακρύνεται πολύ από τη θέση ισορροπίας του και ο ταλαντωτής μας μπορεί να θεωρηθεί αρμονικός, και έχουμε γραμμικά φαινόμενα. / -

The nonlinear optical (NLO) properties were investigated in various extended　π-conjugated chromophores: cyanine and alkyne carbocations; porphyrin dimers; and squaraine compounds that possess electronic, double resonance, and vibronic based NLO properties. In summary: (i) It was demonstrated that the alkyne carbocations have very similar optical properties to traditional cyanine dyes. Our theoretical results establish that the alkyne carbocations, in spite of their significant degree of bond-length alternation, behave in the same way as cyanine dyes. (ii) The nature of the -bridge in porphyrin dimers tunes the electronic coupling strength, which in turn determines the splitting of the energy levels and the (non)linear optical properties. (iii) We have shown that the origin of the lowest TPA-active states in squaraines is dependent on the nature of substituent donor moiety, changing from predominantly electronic to vibronic in character. For all squaraines containing indolinylidenemethyl donors, a vibronic origin for the TPA peak, and the energy and lineshape of the experimentally observed lowest TPA peak in these compounds were confirmed.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.