Foto personale

Maria Cristina MENZIANI

Department of Chemical and Geological Sciences

Content class: Physical chemistry and molecular spectroscopy

Class: CHEMICAL SCIENCES (D.M. 270/04) (Offer 2017)
  • CFU: 12
  • SSD: CHIM/02

Objectives

module A The course aims at providing to the students advanced knowledge of the molecular spectroscopy; from rotational, vibrational and electronic spectroscopy. module B advanced knowledge of quantum chemistry aimed at understanding the formation of chemical bonds in molecules, molecular properties and reactivity.

Prerequisites

Physical chemistry and molecular spectroscopy -module A and B. Basic knowledge of quantum mechanics. Knowledge of the spectral fields relating to different transitions. Knowledge of the concept of atomic mass and isotopic composition. Knowledge of statistical analysis of the experimental data by means and variances and the linear regression parameters.

Course Syllabus

A: Group theory: symmetry of molecules, matrix representations, character of the representations, small and great orthogonality theorem, the tables of characters. Light-matter interaction: time-dependent perturbation theory, Fermi’s golden rule, transition moment, spontaneous emission theory. Rotational spectroscopy: classical and quantum treatment of rotations, selection rules, spectra of linear rigid rotator, intensity of transitions, determination of geometric parameters and permanent dipole moment. Vibrational spectroscopy: vibrational energy levels of diatomic molecules, harmonic oscillator and anharmonic effects, selection rules, vibro-rotational spectra of diatomic molecules. Vibrations in polyatomic molecules, normal modes, the symmetry of the normal modes, the activity of molecular vibrations. Raman spectroscopy. Electronic spectroscopy: classification of electronic states, selection rules, absorption, Frank-Condon factors, fluorescence, phosphorescence. B: Many electrons Hamiltonian: definition and approximations. The Slater determinant. The Hartree-Fock approximation: and the self-consistent field cycle. Definition and examples of a basis set. Key Technical and Practical Points of Hartree–Fock (HF) Theory. The electron correlation problem, brief overview of post-HF methods. Fundamentals of density functional theory (DFT). Models for Condensed Phases. Density matrix and chemical reactivity. Charge distribution. Calculation of observable and comparison with experimental data. Theoretical descriptors in the method of quantitative structure – property relationships. Introduction to the exercises: input and outputs. Using molecular graphics tools for molecule’s manipulation. Exercises : 1) Conformational analysis. 2) Calculation of structural properties, electronic and vibrational properties of molecules in the gas phase, and 3) in the condensed phase. 4) Prediction of observable (eg . pKa , etc ...)

Reference texts

A Appunti del docente. P.W. Atkins, R. S. Friedman, Meccanica Quantistica Molecolare, Zanichelli. W. Struve, Fundamentals of Molecular Spectroscopy, Wiley. I. Baraldi, L’Assorbimento: Introduzione alla spettroscopia elettronica delle molecole poliatomiche. Bonomia University Press B C. J. Cramer Essentials of Computational Chemistry –Theory and Models, Wiley 2004. F. Jensen, Introduction to Computational Chemistry, Wiley, 2007. A.R. Leach Molecular Modelling. Principles and Applications. Addison Wesley Longman 2001 M. Bortoluzzi Approccio qualitative alla Chimica Computazionale Aracne, 2009

Teaching methods

A: Lectures (use of slides and whiteboard) and numerical exercises and laboratory involving the active participation of students. B:Frontal lessons, classroom exercises, guided reading of scientific articles provided by the teacher and collegial discussion. Suggested text-books, scientific articles and educational material made available online in advance. Computer exercises consist of performing the experiment and drafting a brief report; collegial discussion of the results obtained will serve as a self-check on the degree of knowledge / understanding achieved. Non-attending non-attending students must contact the teacher, who will provide guidance on specific supplementary topics to study on textbooks.

Verification of learning

A: A 3 hours written exam consisting of 3 numerical exercises related to the topics of the course. The student will be allowed to use lecture notes and books. This exam will be evaluated with a score of thirty, with possible praise. The evaluation assesses the level of theoretical knowledge (50%), the ability to apply their knowledge (30%), autonomy of judgment (10%) and communication skills (10%). B: The final assessment is based on an interview that consists in discussing the results obtained in one of the class exercises (chosen by the teacher). During the interview will be explored a) the knowledge gained about the subject of the tutorial under discussion (up to 30% of the final score), b) the ability to solve similar problems independently (40%), c) the critical skills (20%), and d) the communication skills acquired by the student (10%).

Expected results

A and B Knowledge and understanding Through lectures, exercises and group discussions, students acquire advanced knowledge of rotational, vibrational and electronic spectroscopy, quantum-mechanical methods for the study of molecules, ii) interpretative models and tools for the understanding and prediction of molecular properties and their response to external perturbations. Applying knowledge and understanding Through lectures, exercises and group discussion students acquire the tools a) to reinterpret in a formal way the knowledge acquired in previous courses in the field of spectroscopy and to plan spectroscopic experiments for the acquisition of molecular information from the analysis of samples macroscopic; b ) independently define quantum protocols for the calculation of properties of isolated and interacting molecules, in the vapor phase and in the condensed phase. Making judgments The course provides students with the language of quantum chemistry applied to time-dependent problems and the interaction of radiation with matter. The student is able to read and understand basic and advanced texts, to successfully address the scientific literature, to elaborate critical evaluation of the results obtained and of the approximations made , choose the most appropriate methods to the problem at hand Communication skills The student acquires the technical jargon that will allow him to communicate with chemical specialists, physicists and scientists of materials, and to translate complex concepts in a language understandable to the non - specialist but ensuring the accuracy of information provided. Written reports and oral examination enable to present data effectively, to discuss them on the basis of the approximations made, to express the concepts with appropriate and concise language and to support an adversarial approach.