PHYSICAL CHEMISTRY II A - L

Learning Objectives

• Physical Chemistry II

  The course aims to provide the basics knowledge of physical chemistry to understand the theoretical models of atomic structure and chemical bond, as well as the principles of molecular spectroscopy and chemical kinetics. At the end of the course, the students will be able to understand and handle the basic principles of quantum mechanics and spectroscopic methods, as well as their applications to the determination of electronic structure and geometry of simple molecular systems. The students will also be acquainted with the basic theories and laws of chemical kinetics, as well as the main methodologies used to theoretically and experimentally studying chemical reactions.

• CHIMICA FISICA II E LABORATORIO (Mod. 2)

  The course aims to offer students specific skills in the field of physical chemistry.

   

  The training is mainly aimed at the development of cognitive competences concerning the basic theoretical principles to be transferred to the technical/practical level, through laboratory experiences.

Detailed Course Content

• Physical Chemistry II

  I – Quantum Mechanics treatment of Atoms and Molecules

  • The dawn of Quantum Mechanics: Postulates of Quantum Mechanics. Wave functions and operators. Schroedinger equation and application to simple systems. Particle in a monodimensional and threedimensional box. Tunneling effect. Harmonic and anharmonic oscillators. Rigid rotator.

  • The hydrogen atom. Helium atom and multielectron atoms. Approximate methods to solve Schroedinger equation: Basics of perturbation methods, variational methods. The orbital approximation. The Hartree-Fock self-consistent field. Correlation energy and the theory of the independent electrons (complex atoms). The Pauli principle and the “Aufbau” methods.

  • Chemical bond and bioatomic molecules. The Born-Oppenheimer approximation. The molecular orbital method and its application to the H₂⁺ molecule. Overlap, Coulombian and exchange integrals: their role in the stability of chemical bonds. Bonding and antibonding molecular orbitals. Multielectron diatomic molecules. Electronic structure in the MO framework. σ e π – orbitals. “Aufbau” method applied to molecular orbitals – Electronic configuration and properties of homonuclear diatomic molecules.
  • Poliatomic molecules. Huckel approximation for simple hydrocarbon molecules(ethylene, butadiene, Cyclobutadiene and benzene). Energy of delocalization. Calculation of charge distributions for a π system - Bonding order - Relationship between bond order and bond length - Hückel method for compounds containing heteroatoms - Experimental evidence for the existence of molecular orbitals.

  • Introduction to the electronic structure of solids.

  II- Radiation-matter interaction and molecular spectroscopy.

  Basic principles of Molecular Spectroscopy.

  Radiation-Matter interaction – Time-dependent Schroedinger equation – Theory of the time–dependent perturbation. Selection rles for radiation-induced transitions – State population and Boltzmann population – Conventional and non-conventional spetroscopies - Born-Oppenheimer approximation in Spectroscopy – Diatomic molecules: separation of vibrational and rotational modes.

  • Rotational spectroscopy – Rotational energetic levels and rotational spectra of diatomic molecules – Classification of rotational features of polyatomic molecules.

  • Vibrational spectroscopy – Vibrational spectra of diatomic molecules and selection rules (harmonic oscillator) – Application of the Harmonic oscillator model – Normal modes of a polyatomicsystem and related vibrational spectra – Vibro-rotational spectra of di-and three-atomic molecules.

  • Electronic spectroscopy – Electronic transitions in diatomic and polyatomic molecules - Selection rules – Franck-Condon Principle and vibronic transitions – UV-Vis spectroscopy in adsorption mode – Photoelectron spectroscopy – Photoelectron spectra of CO and VI group element hydrides – Photoelectron spectra of substituted benzenes.

  • Excited electronic states – Photophysical processes – Einstein coefficients, spontaneous and stimulated emission – Fluorescence spectroscopy – Introduction to laser physics and laser spectroscopy – Introduction to photochemical processes.

  III– Chemical kinetics

  • Rate of chemical reactions – Simple kinetics and related kinetical constants – Integration of simple kinetical equations – Temperature-dependence of the reaction rate – Reaction mechanisms – Elementary reactions – Consecutive and parallel reactions – The principle of the detailed balance – Steady state approximation – Complex reactions – Enzymatic reactions – Oscillatory reactions.
  • Reaction dynamics – Collision theory: collisional cross-section, energetic of the collisions and steric factors – Transition state theory – Experimental methods to study molecular collisions – Angular and velocity distribution of the reaction products in gas phase – Reflection and stripping mechanisms and complex formation model – Reactivity and potential energy surfaces – Ultrafast reactions: femtochemistry processes.
• CHIMICA FISICA II E LABORATORIO (Mod. 2)

  The course is based on several laboratory experiences as shown in the programming section

Textbook Information

• Physical Chemistry II

  P.W.Atkins - Chimica Fisica - Zanichelli, Bologna, 2000.

  D. A. McQuarrie, J. D. Simon, Chimica Fisica: un approccio molecolare, Zanichelli, Bologna, 2000.
  

• CHIMICA FISICA II E LABORATORIO (Mod. 2)
  1. Lesson notes
  2. Physical Chemistry Peter Atkins, Zanichelli