AIMS AND CONTENT

LEARNING OUTCOMES

The teaching aims to illustrate simple applications of modern Quantum Chemistry to Organic Chemistry; in particular, to develop concepts and describe the application of qualitative and semi-quantitative methods for describing the reactivity of organic molecules.

AIMS AND LEARNING OUTCOMES

In particular, the teaching of Organic Physical Chemistry you will find the elements to rationalize organic reactivity through symmetry properties of the reactants and / or products (Woodward-Hoffmann rules) or from the analysis of the reaction profile (theory of frontier orbitals). Furthermore (depending on the time available) the basic elements of quantum mechanics will be provided, aimed at describing the most used ab-initio and semiempirical methods for the calculation of molecular properties.

The student will acquire:

- the ability to identify the different types of pericyclic reactions

- knowledge of the classical and generalized Woodward-Hoffmann rules;

- the ability to apply these rules in the prediction of the products of a pericyclic reaction;

- knowledge of the Klopman-Salem equation and its limits of applicability;

- the ability to apply the Klopman-Salem equation to a varied series of chemical reactions in order to predict their products or discuss their experimental observations in a semi-quantitative way.

- the ability to correlate the Klopman-Salem equation to different predictive models of organic reactivity.

- the knowledge and the ability to apply an effective Hamiltonian model to the calculation of the molecular energies and orbitals of a conjugated organic molecule.

PREREQUISITES

A review of the subjects related to the teaching of Physical Chemistry 3 of the three-year course may be useful, with particular reference to the method: variational, perturbative and to the LCAO theory. Also are required the knoweledge of the Mathematical and Physics teachings of the first years.

TEACHING METHODS

The teaching  corresponds to 6 CFU equivalent to 150 hours of "effective" commitment by the student and is divided as follows: 48 hours of lectures and 102 hours of personal study (the latter include iterative teaching activities - self-evaluation quizzes, discussion forums , in-depth material - which can be chosen independently by the student). The course it is held in Italian language.

In this context, at the discretion of the teacher, self-tests (open-ended, multiple-choice questions or numerical exercises) and / or iterative or non-iterative auxiliary materials are uploaded on the aulaweb page, in order to facilitate the individual study of the students.

SYLLABUS/CONTENT

• Introduction: definition of: transition state,  activated complex, reaction profile, methods for predicting the rectivity of a molecule.
• Symmetry (notes), non-intersection rule.
•  Molecular orbital symmetry conservation: construction of correlation diagrams for some typical types of reactions (cycloadditions, electrocyclic reactions).
• Theory of frontier orbitals: Klopman-Salem equation demostration.
• Applications of the Klopman-Salem equation (eg derivation of the Woodward-Hoffmann rules, HSAB theory).
• Recalls of basic concepts of quantum mechanics.
•  Ab-initio and semi-empirical methods (notes).
•  Modeling of chemical-physical properties of molecular systems.Gaussian, depending on the time available).
•  Interpretation of the output of a typical quantumchemical software (Gaussian, depending on the time available).

Introduction to Quantum Mechanics.
        Crisis of Classical Physics (Illustrated and discussed some of the basic experiments chosen from: atomic model, photoelectric effect, Compton effect, material waves - Davison-Germer experiment, the two-slit experiment, black body and specific heats).
    The Schrödinger equation and postulates of quantum mechanics (the concept of: state of a system, wave function, operator will be introduced. In axiomatic form, the postulates of quantum mechanics will be discussed).
        Introduction to the concept of measurement (hint) and the uncertainty principle.
        Introduction to the Schrödinger equation and analysis of its implications.
    Quantum mechanics applied to simple systems.
        Particle in a potential hole/barrier (hint tunnel effect).
        Particle with rotational motion.
        Harmonic oscillator.
    Approximate methods for solving the Schrödinger equation.
        Variational method (general discussion of the concept, simple applications).
        Perturbative methods (hint).
    Atomic structure (hydrogen atom case, spin, polyelectron atoms, Slater determinants, vector model, spectroscopic notation).
        Hydrogen model and its extension to multi-electron atoms.
        Atomic orbitals.
    Molecular structure (case of diatomic, polyatomic molecules, basic concepts on the nature of bonding, walsh diagram construction, general considerations).
        MO-LCAO method for constructing the polyelectron wave function.
        The covalent bond.
    Applications of quantum mechanics in molecular spectroscopy.
        Radiation/matter interaction.
        Rotational spectroscopy.
        Vibrational spectroscopy.
        Electron spectroscopy.

In accordance with the provisions of the CCS in Chemical Sciences, it is noted that the teaching of Organic Chemistry contributes to the achievement of the following Sustainable Development Goals of the UN 2030 Agenda:

Goal 4: Provide quality, equitable and inclusive education and learning opportunities for all.

Goal 5: Achieve gender equality and empower all women and girls.

RECOMMENDED READING/BIBLIOGRAPHY

1. R.B. Woodward e R. Hoffmann: The Conservation of Orbital Symmetry.
2. I. Fleming: Frontier Orbitals and Organic Chemical Reactions.
3. T. A. Albright, J.K. Burdett e M. Whangbo: Orbital Interactions in Chemistry.
4. A. Szabo e N.S. Ostlund: Modern Quantum Chemistry.

TEACHERS AND EXAM BOARD

LESSONS

LESSONS START

According to the planning of the Degree Course (see the Manifesto, the teaching relates to the second semester).

Class schedule

The timetable for this course is available here: Portale EasyAcademy

EXAMS

EXAM DESCRIPTION

The oral examination is conducted by two tenured professors and has a duration of at least 45 minutes.

Warning! In variation to the normal practice adopted in the CCS, for this course (for the purpose of better organizational management of the exam), enrollment must be made 5 working days before the exam date.

The exam consists of three blocks of two questions (relating  to the Conservation of Symmetry including related topics and to the Theory of Frontier Orbitals including related topics,respectively) of increasing difficulty aimed at verifying the candidate's knowledge, skills and abilities.

The first block, knowledge check, corresponds to 18 points out of 30.

The second block, skills check, corresponds to 8 points out of 30.

The third block, abilities check, corresponds to 4 points out of 30.

ASSESSMENT METHODS

The oral exam is aimed at verifying the achievement of an adequate level of knowledge of the topics developed / discussed during the lessons and the ability to use the correct terminology combined with the consistency of exposure of the concepts and methodologies described in the teaching.

In particular, through a series of questions of increasing difficulty, the candidate's ability to apply the theory of Conservation of Symmetry and the theory of Frontier Orbitals will be assessed in the description of the reactivity properties of molecules in relation to specific model cases and / or exercises.  As indicated in the exam descriptions, these are three blocks of questions; the first aimed at verifying the acquisition of the notional contents of the course (knowledge), the second aimed at verifying the ability to apply these contents to model exercises (skills) and finally the third aimed at verifying the candidate's ability to solve exercises of a general nature, relating to molecular reactivity, applying the knowledge and skills acquired (abilities).

Overcoming the first block allows the candidate to acquire a maximum of 18 out of 30 points (therefore a maximum score of 18/30). If the score obtained in this phase is such as not to guarantee sufficiency as a final grade, the commission will invite the candidate to withdraw and deepen the study of the subject also making use of further explanations by the teacher before repeating the exam.

Overcoming the second block allows the candidate to acquire a maximum of 8 out of 30 points (therefore, also considering the previous block, with a maximum score of 26/30).

Overcoming the third block allows the candidate to acquire a maximum of 4 out of 30 points (therefore, also considering the previous block, with a maximum score of 30/30).

The candidate has the right to decide whether to face the two blocks following the first one or to stop and obtain the total score obtained as a vote.

Examples of a possible exam course:

Case (a) the candidate does not fully pass the first block. The score acquired and the progress of the exam is such as to make the commission believe that the minimum score of 18/30 cannot be acquired; the candidate is invited to withdraw.

Case (b) the candidate fully passes the first block, acquires the score of 18/30. He decides to move on to the second block which does not fully pass acquiring a vote between 18-26 / 30 and decides not to continue. The score obtained will correspond to the final mark.

Case (c) the candidate fully passes the first block, acquires the score of 18/30. He decides to move on to the second block which he does not pass fully, acquiring a score between 18-26 / 30 and decides to want to move on to the third block. In this case you will be able to acquire a maximum of 4 out of 30 points, and the total score obtained will correspond to the final mark.

Note: if the candidate decides not to follow the commission's invitation to withdraw (if the need arises) and the final mark obtained is insufficient, it will be registered.

FURTHER INFORMATION

Students who have valid certification of physical or learning disabilities on file with the University and who wish to discuss possible accommodations or other circumstances regarding lectures, coursework and exams, should speak both with the instructor and with Professor Sergio Di Domizio (sergio.didomizio@unige.it), the Department’s disability liaison.

Erasums students are given the possibility upon request to take the exam in English and at the discretion of the commission the exam may be given in written mode.