Quantum-chemical investigations of second- and third-order nonlinear optical chromophores for electro-optic and all-optical switching applications

The past decades have witnessed the development of new materials with large nonlinear optical (NLO) properties, which have made them attractive candidates for a broad spectrum of applications in the electro-optic and photonic fields (e.g., telecommunications and computing). A deeper understanding of the relationship between, on the one hand, the electrical and (linear and nonlinear) optical properties and, on the other hand, the chemical structure has proven useful for the rational design of new efficient NLO materials. Developing such an understanding has attracted major interest in the scientific community worldwide in both academia and industry.; Traditional electro-optic and photonic technologies based on inorganic materials, such as LiNbO3, face inherent limitations leading the commercial devices based on such materials to approach practical limits. Although organic materials have their own deficiencies, a broader range of intrinsic advantages and potential design suggests that for many applications, organic technologies provide attractive alternatives to those based on inorganic platforms.; The development of commercial devices of high quality has been helped via the establishment of multidisciplinary research teams combining: (i) theoretical modeling using quantum-chemical computational calculations; (ii) organic synthesis; (iii) optical characterization; and (iv) device fabrication. In this dissertation, quantum chemistry is used to evaluate the second- and third-order NLO properties of series of new chromophores. We take advantage of a feedback loop with experimental teams to understand the relationship between NLO properties and chemical structure, with the hope of assisting the rational design of new and efficient NLO chromophores.