OVERVIEW

Physical Organic Chemistry studies the reactivity of organic molecules through theoretical and conceptual models derived from physical chemistry and quantum mechanics.
In continuity with basic training, the course provides interpretative tools for understanding and predicting reaction mechanisms, with particular emphasis on approaches based on molecular orbital symmetry and on the interaction between reacting species.
The course is positioned within the Master’s Degree programme as advanced theoretical‑modeling support for organic chemistry.

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

Attendance and active participation in lectures, self‑assessment activities and possible exercises, together with individual study, will enable students to acquire the knowledge, competences and skills described below.

At the end of the course, the student will be able to:

1. Describe and critically analyse the fundamental concepts of physical organic chemistry related to molecular reactivity, including transition state, activated complex and reaction profile, distinguishing between energetic and orbital‑based descriptive approaches.

2. Understand and apply the principles of molecular orbital symmetry and orbital symmetry conservation theory, identifying and classifying the main types of pericyclic reactions and predicting their outcomes on the basis of Woodward–Hoffmann rules, both in their classical and generalized formulations.

3. Understand and use frontier molecular orbital theory, including the derivation and physical meaning of the Klopman–Salem equation, applying it to the analysis and prediction of the reactivity of organic molecular systems across a variety of model cases.

4. Correlate and critically compare the Klopman–Salem equation with other predictive models of organic reactivity (e.g. HSAB‑type approaches), highlighting their domains of applicability and interpretative limits.

5. Apply basic concepts of quantum mechanics to the semi‑quantitative description of organic molecules, using effective Hamiltonian models to calculate molecular energies and orbitals, and critically interpret the results of ab initio and semi‑empirical calculations.

In addition, at the end of the course the student will have developed:

• communication skills, being able to clearly, rigorously and coherently present concepts, models and results of physical organic chemistry using appropriate scientific terminology;
• autonomy of judgement, critically interpreting theoretical models and computational results in relation to molecular reactivity phenomena;
• autonomous learning skills, useful for advanced activities in molecular modelling and for further study and research in the chemical field.

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 variational method, the perturbative method and to the LCAO theory.

Also are required the knoweledge of the Mathematical and Physics teachings of the first years.

TEACHING METHODS

Teaching methods are designed in coherence with the expected learning outcomes and aim at the integrated development of theoretical knowledge, applied competences and critical analysis skills related to molecular reactivity.

The course corresponds to 6 ECTS credits, equivalent to 150 hours of total student workload, divided into 48 hours of lectures and 102 hours of individual study.
Individual study includes iterative learning activities such as self‑assessment quizzes, discussion forums and supplementary learning materials (videos, articles, etc.), which are strongly recommended and may be chosen autonomously by the student.

Lecture notes are normally made available on the AulaWeb platform in coordination with classroom activities.

The course, in order to meet specific needs such as student workers, has a one-to-one correspondence with a related website (made available by the University -AulaWeb service) where it is possible, through a substantially diachronic method, to access the teaching material provided: handouts, auxiliary material (optional) forin-depth study of an iterative and/or non-iterative type, discussion forum (student-teacher, student-student) for the topics associated with each lesson, self-assessment tests/quizzes.

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).

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.

Optional:

4) A. Szabo e N.S. Ostlund: Modern Quantum Chemistry.

TEACHERS AND EXAM BOARD

LESSONS

LESSONS START

According to the timetable reported here.

Class schedule

The timetable for this course is available here: Portale EasyAcademy

EXAMS

EXAM DESCRIPTION

The exam is oral and 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 teaching (in order to better manage the exam) registration must be done 5 working days before the exam date.
.
The oral exams consists of three phases, each with two questions (relating respectively to the Conservation of Symmetry including related topics and to the Theory of Frontier Orbitals including related topics) of increasing difficulty aimed at verifying the knowledge, skills and abilities acquired by the candidate.

• In the first phase, verification of knowledge, a maximum of 18 points out of 30 can be acquired.
• In the second phase, verification of skills, a maximum of 8 points out of 30 can be acquired.
• In the third phase, verification of skills, a maximum of 4 points out of 30 can be acquired.

Note: for students with disabilities or DSA, please refer to the Other Information section.

ASSESSMENT METHODS

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

In particular, the candidate's ability to apply the Conservation of Symmetry and the Frontier Orbitals  theories in the description of the reactivity properties of molecules in relation to specific model cases and/or exercises will be assessed through a series of questions of increasing difficulty.

As indicated in the exam methods, these are three blocks of questions; the first aimed at verifying the acquisition of the notional contents of the teaching (knowledge), the second at verifying the ability to apply such contents to model exercises (skills) and finally the third aimed at verifying the candidate's ability to solve general exercises, relating to molecular reactivity, applying the knowledge and skills acquired (ability).

Passing the first part allows you to acquire a maximum of 18 out of 30 points.
If the score obtained in this phase is such that it does not guarantee a passing grade as a final grade, the commission will consider the test as failed and will advise the candidate to study the subject in greater depth, also availing himself of further explanations from the teacher before repeating the exam.

Passing the second part allows you to acquire a maximum of 8 out of 30 points
These will be added to those obtained in the knowledge test.

Passing the third part allows you to acquire a maximum of 4 out of 30 points
These will be added to those obtained in the knowledge and skills test.

The candidate has the option of deciding whether to take the two blocks following the first or to stop and obtain the total score obtained as a grade.

Examples of a possible exam progress:

Case (a): the candidate does not pass the first block. The score acquired and the progress of the exam is such that the commission believes that the minimum grade of 18/30 cannot be acquired; the test is considered failed. The score obtained will correspond to the final grade.

Case (b): the candidate passes the first block. Decides to move on to the second block and subsequently decides not to continue in the third. The total score obtained in the two sections will correspond to the final grade.

Case (c): the candidate passes the first block. Decides to move on to the second block and decides to move on to the third block. In this case, the total score obtained in the three sections will correspond to the final grade.

FURTHER INFORMATION

Erasum students are given the opportunity, upon request, to take the exam in English and, at the discretion of the commission, the exam may be administered in written form.

For students with DSA and/or disabilities, please refer to the University regulations, see dedicated web page on the University site.

For any further information not included in the teaching sheet, please contact the teacher.