MOLECULAR SPECTROSCOPY

The course is among the core educational activities of Master's Degree Programme in Sustainable Chemistry and Technologies. The aim of this Master's Degree is to provide an in-depth scientific knowledge and solid understanding of advance aspects, thus allowing the Master’s graduates to rationalize chemical processes and to elaborate and apply original ideas, whether in a context of research or of an applicative/industrial environment.
Within this framework, the course will provide a deep and solid understanding of both the theoretical and the specialist concepts of several spectroscopic techniques belonging to different regions of the electromagnetic spectrum, from the rotational spectroscopies to the magnetic ones (NMR and EPR), also providing a detailed discussion on some of their modern applications.

At the end of the course students should:
- have a solid Knowledge and deep understanding of the correct spectroscopic formalism to be used, and of the theoretical concepts of both optical spectroscopies and magnetic ones (NMR, both mono- and bi-dimensional, as well as EPR, and their corresponding formalism), and some of their modern applications (studies on surfaces, structural determinations);
- be able to apply the correct formalism for analyzing the different spectroscopic phenomena (and their corresponding data in their spectral range), and to discuss the corresponding spectroscopic techniques and applications using all the theoretical concepts treated during the course;
- be able also to judge and compare the performances and the applicability of the different spectroscopic techniques in view of the chemical problems to be solved and/or the researches to be carried out.

The students should know (and be able to apply) the basic concepts of calculus (vectors, differential and integral calculus of more than one variable functions) and physics (classical electromagnetism).

BASIC CONCEPTS OF QUANTUM MECHANICS
Eigenvalues and eigenfunctions. Energetic levels and transitions. Energy diagrams. Boltzmann statistics.
Induced absorption, induced and spontaneous emission, and their corresponding Einstein coefficients. Electric and magnetic transition moments. General and specific selection rules. Classification of spectroscopies: optical and magnetic.
The rigid rotor model, its eigenvalues and eigenfunctions. The harmonic oscillator model: its eigenvalues and eigenfunctions. Spectroscopy of the harmonic oscillator. Extension to polyatomic system: normal modes of vibration and their description.
ROTATIONAL AND INFRARED SPECTROSCOPIES
Classification of molecules according to their principal moments of inertia: linear molecules, symmetric tops, asymmetric and spherical tops. Selection rules. The effects of centrifugal distortion on the rotational spectrum. The effects of isotopic substitution. Examples and uses of microwave spectra.
Infrared (IR) spectroscopy: harmonic treatment and the anharmonic corrections. Polyatomic molecules, selection rules, and ro-vibrational spectra. Examples of infrared spectra. Discussion of some relevant experimental techniques and their application for solving chemical problems, and for the studies of surfaces: laser sources and Cavity RingDown Spectroscopy (CRDS), Attenuated Total Reflection (ATR) IR spectroscopy, Surface Enhanced InfraRed Absorption Spectroscopy (SEIRAS), Reflection-Absorption IR Spectroscopy (RAIRS), and Diffuse Reflectance IR Spectroscopy (DRIFT). Sum Frequency Generation – Vibrational Spectroscopy (SFG-VS): basic concepts an application to the studies of surfaces.
NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY
The nuclear spin and its properties. Bloch phenomenological equations and their solutions in both the laboratory (fixed) axes and the rotating axes. Relaxation processes: spin-lattice and spin-spin mechanisms. Pulses in NMR spectroscopy. The time-dependent signal and its Fourier Transform (FT). General description of the instrument. Phase correction.
Descriptions of the main Hamiltonians employed for describing NMR spectroscopy. NMR in isotropic medium. Experimental measurements of spin-lattice and spin-spin relaxation processes. Product operator formalism. In-phase and anti-phase magnetization and their interconversion. Magnetization transfer through scalar coupling: product operator analysis. Example of calculation employing product operators: the spin-echo pulse sequence and heteronuclear coherence transfer using Insensitive Nuclei Enhanced by Polarization Transfer (INEPT).
Bi-dimensional NMR (2D-NMR). Description of a general bi-dimensional experiment. The COSY (Correlation SpectroscopY) experiment. Multiple quantum terms. Coherence-order calculation. Evolution of multiple quantum terms. Description of the Double Quantum Filtered COSY (DQF-COSY) experiment. Description of HETero-nuclear CORrelation spectroscopy (HETCOR), Heteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Multiple Bond Coherence (HMBC). Examples and applications.
ELECTRON PARAMAGNETIC RESONANCE (EPR) SPECTROSCOPY
The electron spin. Spin labels and spin probes. Description of the instrument. Descriptions of the main Hamiltonians employed for describing EPR spectroscopy. Anisotropy of the g-tensor and of the hyper-fine interaction. Examples and uses of EPR spectra.

For the optical spectroscopies, the textbook mainly used in the course is
J. M. Hollas, “Modern Spectroscopy”, 4th edition, Wiley, 2003.
For the magnetic spectroscopies, the textbook mainly used in the course is
N. E. Jacobsen “NMR SPECTROSCOPY EXPLAINED: Simplified Theory, Applications and Examples for Organic Chemistry and Structural Biology”, John Wiley & Sons, 2007.

Some other suggestions on EPR topic:
A. Lund, M. Shiotani, S. Shimida, “Principles and Applications of ESR spectroscopy”, Springer, New York, 2011.

Oral examination (about 30’).
It consists in a series of questions about the different topics covered in the course; the student will be asked also to apply the different formalisms for describing a given spectroscopic experiment, and to justify the corresponding outcomes.

Lectures coupled to the use of some dedicated software packages.
The slides employed during each lecture (and the corresponding supplementary material together with examples about how to describe the spectroscopic data) will be downloadable from the MOODLE web pages.

Italian

Accessibility, Disability and Inclusion

Accommodation and support services for students with disabilities and students with specific learning impairments:
Ca’ Foscari abides by Italian Law (Law 17/1999; Law 170/2010) regarding support services and accommodation available to students with disabilities. This includes students with mobility, visual, hearing and other disabilities (Law 17/1999), and specific learning impairments (Law 170/2010). In the case of disability or impairment that requires accommodations (i.e., alternate testing, readers, note takers or interpreters) please contact the Disability and Accessibility Offices in Student Services: disabilita@unive.it.

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