Photoactive materials - MC240P17

• Title: Fotoaktivní materiály
• Czech title: Fotoaktivní materiály
• Guaranteed by: Department of Inorganic Chemistry (31-240)
• Faculty: Faculty of Science
• Actual: from 2018 to 2018
• Semester: winter
• E-Credits: 3
• Examination process: winter s.:
• Hours per week, examination: winter s.:2/0, Ex [HT]
• Capacity: unlimited
• Min. number of students: unlimited
• 4EU+: no
• Virtual mobility / capacity: no
• State of the course: taught
• Language: Czech
• Note: enabled for web enrollment
• Guarantor: prof. RNDr. Jiří Mosinger, Ph.D.
• Teacher(s): prof. RNDr. Jiří Mosinger, Ph.D.

Annotation

English

Last update: doc. RNDr. Vojtěch Kubíček, Ph.D. (22.03.2018)

Overall mechanism and elementary reactions. Characteristics of elementary reactions. The relations between the rate law and the kinetics vs. thermodynamic aspects of mechanism. Molecular collision and transition state theory. Frontiers electrons and the frontier orbitals. HOMO - LUMO interaction. The conservation of orbital symmetry (Wigner - Witmer and Woodward - Hoffmann rules). Spin conservation rules.
Group transfer and atom-transfer reactions (dissociative, associative and interchange mechanism). Electron-transfer reactions (outer and inner-sphere transfer mechanism). Introduction to photochemistry. Basic photophysical and photochemical processes.
The course is designed for Master and PhD students.

Czech

Last update: RNDr. Jiří Schulz, Ph.D. (23.03.2018)

Cílem přednášky je seznámit studenty s úvodem do fotochemie a její aplikací na nano(materiály).

Literature

Last update: RNDr. Jiří Schulz, Ph.D. (23.03.2018)

• Rachel C. Evans, Peter Douglas, Hugh D. Burrows: Applied Photochemistry, Springer 2013.

  Petr Klán: Organická fotochemie, Masarykova universita v Brně, 2001

  Nicholas J.Turro: Modern Molecular Photochemistry, University Science Books, 1991.

  Petr Klán, Jakob Wirz: Photochemistry of Organic Compounds, Wiley, 2009.

Requirements to the exam

Last update: prof. RNDr. Jiří Mosinger, Ph.D. (24.10.2019)

Úspěšné absolvování písemné zkoušky + ústní přezkoušení

Syllabus

English

Last update: doc. RNDr. Vojtěch Kubíček, Ph.D. (22.03.2018)

1. Overall mechanism and elementary reactions. Characteristics of elementary reactions. The relations between the rate law and the kinetics vs. thermodynamic aspects of mechanism.
2. Molecular collision and transition state theory.
3. Frontiers electrons and the frontier orbitals. HOMO - LUMO interaction.
4. The conservation of orbital symmetry (Wigner - Witmer and Woodward - Hoffmann rules). Spin conservation rules.
5. Selected problems from kinetics and thermodynamic of reactions. The relation between the "rate law" and the mechanism of reaction. Steady-state approximation, numeric methods, mathematic a experimental difficulties in determination the mechanism of reaction. Thermodynamics of transition state. Calculation of DH#, DS#, DV#
6. Classifications of inorganic reactions. Group transfer and atom-transfer reactions. Substitution mechanisms (dissociative, associative and interchange reactions). Empirical criteria for deciding the mechanism of substitution. Chelate ring formation. Coordination sphere expansion, addition and condensation. Tetrahedral substitution.
7. The structure correlation method in tetrahedral substitution. Substitution in square planar complexes. Influence of central atom, leaving and entering ligand and the trans-effect on rate of the substitution. Pathways in square planar substitution using model HOMO-LUMO. Substitution of octahedral complexes. Stereochemical changes during substitution.
8. Acid and base hydrolysis in octahedral complexes Co(III). Associative and dissociative mechanism in octahedral complexes Cr(III). Lability of aqua-ions. Insert reactions. a-H transfer. Topological mechanisms (Berry mechanism, inversion configuration in pyramidal molecules, trigonal twist). Inter- and intramolecular proton transfer. Covalent hydrates, pseudobase formation.
9. Electron transfer reactions (ET). Relation between ox. number, molecular geometry and the composition of the first coordination sphere. Tendency toward electroneutrality. Formal ox. number and real charges. Mechanisms and "rate law" for ET. Classification of ET.
   Direct and indirect ET. "Solvent mediation" and solvated electrons. Redox reactions of oxo and hydroxo compounds. Acid and base catalysis. Expansion of coordination sphere and ET without change of structure. Oxidative addition.
10. Reductive elimination. Two-electron transfer. Mapping the course of a bimolecular redox. reaction. Franck-Condon princip. Optical and thermal ET. A donor-acceptor model.
11. Introduction to photochemistry. The base of photochemistry. Absorption of irradiation, vertical excitation in Franck-Condon model. Jabloňski diagram. Radiative and nonradiative processes. Time, speed and energy in photochemistry. Spectral regions of photochem. interest. Shape of molecules in excited states. Destination of excited molecules (energetic profile). The ways of deactivations of excited molecules. Basic photochemical laws and rules.

Czech

Last update: RNDr. Jiří Schulz, Ph.D. (23.03.2018)

Přednáška zahrnuje následující tématické bloky: 

1.Úvod do fotochemie.

Základní termíny, charakterizace fotofyzikálních a fotochemických dějů, jejich základní popis, kvantové výtěžky, fotochemické zákony a pravidla.

2. Fotochemické procesy - vznik a vlastnosti excimerů, exciplexů, fotoindukovaný přenos elektronu, difúzně řízené reakce. Kinetika a pravidla. Reaktivita excitovaných stavů.

3. Absorpce a emise.

Excitace molekul a jejich následná relaxace. Kinetika a pravidla.

Absorpční a emisní (luminiscenční) vlastnosti molekul a materiálů: UV/Vis, emisní a excitační spektroskopie

5. Fotoindukované jevy ve složitých systémech, (nano)materiálová aplikace (polovodičové materiály, kvantové tečky, OLED, solární články, „Up-conversion“ materiály).

6. Molekulární kyslík a jeho význam pro tvorbu ROS.

7. (Nano)materiály generující ROS, aplikace.