Soutenance publique de thèse de doctorat en Sciences chimiques - François Mairesse

Solid State Quantum Chemical Calculations and Analysis of the Second-Order NLO Responses of Macroscopic Systems

Jury

• Prof. Francesca CECCHET (UNamur), Présidente
• Prof. Benoît CHAMPAGNE (UNamur), Secrétaire
• Prof. Frédéric CASTET (UBordeaux)
• Prof. Luc HENRARD (UNamur)
• Prof. Vincent LIÉGEOIS (UNamur)
• Prof. Lorenzo MASCHIO (UTorino)
• Prof. Janine GEORGE (BAM)

Résumé

This thesis presents several advances in the prediction and the understanding of the linear and second-order nonlinear optical (NLO) properties of macroscopic systems, including crystalline semiconductors, statistically disordered crystals, finite crystals, and dynamic interfacial systems. This also includes an investigation of a straightforward yet efficient structure optimization method. After a contextualizing historical introduction, the classical as well as the quantum mechanical mathematical descriptions of optics in the homogeneous (but eventually anisotropic) condensed phase are presented, starting from the Maxwell's equations up to the time-dependent density functional theory (TDDFT) level. Afterwards, a series of publications are presented, discussing, respectively, i) the crystal structure optimization method at the density functional theory (DFT) level with inclusion of a posteriori London interaction correction to the energy and energy gradient, ii) the fine-tuning of the linear and nonlinear optical properties calculation method at the TDDFT level, in terms of basis function sets, exchange-correlation functional (XCF), Brillouin zone sampling, lattice summation truncation, and convergence criteria, iii) the prediction and comparison to experimental values of rotationally averaged NLO properties of cellulose nanocrystals in solution, iv) the rationalization of the NLO response origin of the water-air interface involving a deep structural analysis of the liquid interface and v) the linear and nonlinear optical properties evolution of anil-based molecular switch crystals upon increasing partial switching. Then, the conclusions are presented along with the perspectives of this thesis work. As a complement to the theoretical chapter, the mathematical expressions of several XCFs and the derivation of the related potentials are provided.

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