Luminescent properties of the dye molecules can be influenced by the environments as well as intermolecular interactions. Suitable control the aggregation can be useful for optoelectronic device applications. In this thesis, we investigate the spectroscopic properties of dye molecule, DiI_C18, in solutions. Solvents and concentrations are used to control the degree of aggregation. Absorption and emission are used to probe the properties. We use water, methanol, and ethylene glycol as key solvents to control the aggregation effects, especially the methanol solution mixing with water. As the concentration increased, the change of the absorption spectra are observed, which is caused by the aggregation between molecules. Two types of aggregations: head-to-tail structure and parallel structure, are proposed. Head-to-tail structure behaves red-shifted spectrum, and a corresponding shorter decay lifetime. On the contrary, parallel structure aggregation exhibits blue-shifted absorption spectrum and a longer fluorescence lifetime. Both structures are observed at different period after mixing. Only monomer exists in the methanol solution, even at high concentration. However, after missing with water, parallel structure aggregates are formed. Head-to-tail structure aggregates are formed after a much longer period, usually several hours after the mixing. These aggregates not only have different photo-physical properties. After high light intensity illumination, parallel structures are easier to turn into non-fluorescent structures, while head-to-tail structures last a longer period. Monomer structures exhibit the longest period. This provides additional evidence for the formation of different structures in the mixing solutions.

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