# PHYSICAL CHEMISTRY II M - Z

**Academic Year 2017/2018**- 2° Year

**Teaching Staff**

- Physical Chemistry II and Laboratory M-Z (Mod 1):
**Cristina SATRIANO** - CHIMICA FISICA II E LABORATORIO (Mod. 2):
**Luisa D'URSO**

**Credit Value:**12

**Scientific field:**CHIM/02 - Physical chemistry

**Taught classes:**28 hours

**Exercise:**24 hours

**Laboratories:**72 hours

**Term / Semester:**2°

## Learning Objectives

**Physical Chemistry II and Laboratory M-Z (Mod 1)**The course aims to provide the physico-chemical basic knowledge for understanding the chemical bond, the molecular spectroscopy and the chemical kinetics. At the end of the course the student will be able to understand the basic principles of quantum mechanical and spectroscopic methods and their application to the determination of the electronic and geometric structure of simple molecular systems, the laws and the basic theories of chemical kinetics as well as the main methods for the theoretical and experimental study of chemical reactions.

**CHIMICA FISICA II E LABORATORIO (Mod. 2)**The goal of Laboratory activity is to develop the capabilities of observation and analysis through experimental procedures aimed at the determination of chemical-physical parameters.

## Detailed Course Content

**Physical Chemistry II and Laboratory M-Z (Mod 1)****I - Quantum description of atoms and molecules structure.**Crisis of classical physics and the origin of quantum theory. Postulates of quantum mechanics. Wave functions and operators. Schroedinger equation. The particle in a potential well. Harmonic oscillator and anharmonic. Rigid rotator. The hydrogen atom. Approximate methods for solving the Schroedinger equation: perturbation methods; variational method. The helium atom. Angular momentum and spin states. Variational principle and mean field theory for atoms with more electrons. Orbital approximation. Method of Hartree-Fock. Correlation Energy. Independent Electron Theory for complex atoms. Pauli principle. Aufbau.

The chemical bond and diatomic molecules. Born-Oppenheimer approximation. The molecular orbital method and application to the hydrogen molecule ion. Overlap integrals, Coulomb and exchange and their contribution to the stability of the chemical bond. Molecular orbitals of bonding and antibonding. Diatomic molecules with more than one electron. Electronic structure in the MO diagram. Orbital σ and π - Application of the method of molecular orbitals aufbau - Electronic configuration and properties of diatomic homonuclear molecules.

Polyatomic molecules. The Huckel method. Relocation Energy. Calculation of charge distributions for a π system. Bond order π and total. Extension of the Hückel method to compounds containing heteroatoms. Experimental evidence of the existence of molecular orbitals. Introduction to electronic structure of solids.

**II - Light-matter interaction and molecular spectroscopy.**Basic principles of molecular spectroscopy. Interaction electromagnetic radiation with matter. Time-dependent perturbation theory. Born-Oppenheimer approximation for spectroscopy.

Rotational Spectroscopy. energy levels rotational and rotational spectra of diatomic molecules. Classification of molecules from a rotational standpoint and their spectra: linear rotators, symmetrical oblates and prolates, spherical, asymmetrical.

Vibrational spectroscopy. Vibrational spectra of diatomic molecules and selection rules according to the harmonic oscillator model. Application of the anharmonic oscillator model - Normal modes of a polyatomic system and vibrational spectra. Vibro-rotational spectra of two-, and triatomic molecules.

Electronic spectroscopy. Electronic transitions in diatomic and polyatomic molecules. Selection rules. Franck-Condon principle and vibronic transitions. Photoelectron spectroscopy. Electronic excited states. Photophysical processes. Einstein coefficients, spontaneous emission and stimulated emission. Fluorescence Spectroscopy.

Lasers and laser spectroscopy. Photochemical processes.

**III - Chemical Kinetics.**Rate of chemical reactions. Kinetic laws and kinetic rate constants. Integration of simple kinetic equations. Dependence of the reaction rate from the temperature. Reaction mechanisms. Elementary reactions. Consecutive and parallel reactions. Detailed balance principle. Approximation of the stationary state. Complex reactions. Enzyme kinetics. The dynamics of reactions. Collision theory: sphere of collision, shock section, shock energy and steric factor. Transition state theory. The experimental study of molecular collisions. Angular distribution and of the speed of the reaction products. Bounce mechanisms, stripping and with complex formation. Potential energy surfaces. The study of ultrafast reactions: femtochemistry.

**CHIMICA FISICA II E LABORATORIO (Mod. 2)**Kinetic studies by UV-Vis spectrometry: acetone iodination

Conductometric kinetics: ethyl acetate hydrolysis

Fluorescence spectroscopy: verification of Stern-Volmer Ru (bpy) 3] Cl2 law in presence of a quencher (Q) phenothiazine

FT-IR spectroscopy: FT-IR spectra of solid, liquid and gaseous carbonyl compounds.

Electronic Spectra: I2 absorption

Electronic spectra: absorption of conjugated polyenes

Contact angle: calculation of free surface energy

UV-Vis spectroscopy: Photodegradation of organic contaminants by the use of titanium dioxide nanoparticles

## Textbook Information

**Physical Chemistry II and Laboratory M-Z (Mod 1)**- Handouts and lecture slides provided by the teacher.
- P. Atkins, J. de Paula, R. Friedman -
**QUANTA, MATTER, AND CHANGE: A MOLECULAR APPROACH TO PHYSICAL CHEMISTRY**-W.H. FREEMAN AND COMPANY New York.D.A. - Mc.Quarrie, J.D. Simon –
**CHIMICA FISICA un approccio molecolare**- Zanichelli - P. Atkins, J. de Paula -
**PHYSICAL CHEMISTRY 9th Ed**- W.H. FREEMAN AND COMPANY New York / P.W. Atkins, J. de Paula -**Chimica fisica**- Zanichelli - J.M. Hollas,
**MODERN SPECTROSCOPY**- Wiley

**CHIMICA FISICA II E LABORATORIO (Mod. 2)**Atkins De Paula - Chimica Fisica - Zanichelli