SOLID STATE CHEMISTRY MOD.A
To undertake Module A, a fundamental prerequisite is a consolidated knowledge of structural chemistry and of the theory of X-ray diffraction by crystals.
Fundamental prerequisites to undertake Module B are:
• a consolidated knowledge of all the basic and advanced topics of general and inorganic chemistry (e.g. metals, inorganic oxides, inorganic halogenides, coordination compounds, ligands and their electronic properties, crystal field theory) and of the basics of organic chemistry (e.g. oxygen-, nitrogen-, phosphorous- and sulphur-donor aliphatic and aromatic compounds; electron-acceptor aliphatic and aromatic compounds);
• knowledge of fundamentals of mathematics (e.g. integral, exponential, logarithm, derivative, vector, tensor, matrix, etc.) and physics (e.g. force, pressure, speed, potential energy, kinetic energy, etc.).
Module A of this course aims to put into practice the theoretical knowledge acquired during the course of Structural Chemistry, with particular reference to structure solution procedures through conventional single-crystal diffraction techniques, and innovative powder diffraction methods. Knowledge expected from the students after the course include the understanding of data collection strategies and of analytical/computational procedures aimed to the determination of the structure and microstructure of mono- and poly-crystalline samples.
Module B of this course introduces, by way of non-exhaustive examples, some aspects of the vast world of solid-state chemistry, encompassing both inorganic and organic chemistry. The course is appropriate for those students who, irrespective of their curriculum, are interested into the comprehension of the relationships between crystal structure and functional properties (magnetic, electronic, optic, thermal, spectroscopic properties,…). As an outcome, students are expected to understand a number of solid-state functional properties of inorganic and organic compounds; the relationships between functional properties and the structural aspects; the correlations existing between functional properties and practical applications, also at an industrial level.
Module A:
Diffraction theory: an overview; Patterson synthesis; Structure solution and refinement from single-crystal diffraction data; comparative structural analysis and use of crystallographic databases; powder diffraction: theory and instruments; qualitative analysis; quantitative analysis; indexing; the Rietveld method.
Module B:
1. Polymorphism: the birth and evolution of the concept of polymorphism and its nomenclature; industrial importance and frequency; structural origin; thermodynamic description of monotropic and enantiotropic systems; examples of polymorphic organic, organometallic and inorganic systems.
2. Magnetic properties of solid-state materials: introduction on diamagnetism, paramagnetism, ferromagnetism, antiferromagnetism, ferrimagnetism. Magnetic susceptibility; Curie and Curie-Weiss laws. Spin, orbit and total magnetic moments. Ferromagnetism: location in the periodic table; behavior of d and f transition elements; magnetic domains; saturation magnetization; hysteresis loops; permanent magnets; examples. Antiferromagnetism, superexchange; examples.
3. Intercalation compounds: historical evolution and nomenclature; mechanisms of intercalation; synthesis of intercalation compounds; classes of intercalation compounds: metal dichalcogenides, metal oxyhalides, metal oxides, zirconium phosphates, graphite, clays.
4. Non-linear optical properties in solid-state materials: notions of linearity and non-linearity; origin and nature of the phenomena of non-linear optics: sum-and difference-frequency generation; second- and third-harmonics generation, electro-optic effect; measurement techniques; compounds for second-order non-linear optics: inorganic, organic and metallorganic compounds (the "push-pull effect", the "salt method", the "two-state model").
5. Electrical properties of solid-state materials: dielectricity, electronic conduction, semiconduction, ionic conduction, superconductivity. Ionic conduction: introduction; conduction mechanisms; electrolytes; applications of solid electrolytes.
Modules A and B do not require the adoption of specific textbooks. Both Professors use teaching material prepared ad hoc, including the slides proposed during the lessons and book chapters exclusively in English, as an integration to the lectures.