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 also providing a detailed discussion on some of their modern applications in the fields of chemistry, biochemistry and biology.

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 advanced optical (linear and non-linear) and magnetic spectroscopies (NMR as well as EPR, the pulse sequences formalism and the corresponding analysis based on product operators), and some of their modern applications (dynamics of chemical processes, studies on atmospheric pollutants in real-time, investigations on surfaces and interphases, adsorption processes, structural determinations and analysis of processes also for biochemical and biological applications);
- be able to apply the correct formalism for analyzing the different spectroscopic phenomena (and their corresponding data in their spectral range). In details, the students will be able to apply physical and quantum-chemical concepts to optical spectroscopies (both linear and non-linear) as well as to magnetic spectroscopies (describing the experiment on the basis of the pulse sequences as defined by IUPAC and applying the product operator formalism to both predict the results and improve the sequences also varying the experimental parameters).
- be able to discuss the corresponding spectroscopic techniques and interdisciplinary applications (using all the theoretical concepts treated during the course) for investigating chemical processes, atmospheric pollutants (in real-time), surfaces and interphases, adsorption processes, structural determinations and analysis of processes also for biochemical and biological applications;
- be able also to judge and compare the performances, the issues 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;
- be able to communicate the knowledge learned, the formalism employed, and the results of its application using appropriate terminology;
- be able to learn advanced topics by reading scientific articles.

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), physics (classical electromagnetism), of quantum chemistry and of spectroscopy.

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.
ROTATIONAL AND INFRARED SPECTROSCOPIES
Classification of molecules according to their principal moments of inertia. The effects of centrifugal distortion on the rotational spectrum. The effects of isotopic substitution. Examples and uses of microwave spectra in chemistry.
Infrared (IR) spectroscopy: harmonic treatment, normal modes and the anharmonic corrections. Ro-vibrational spectra. Basic concepts on Raman spectroscopy, principles and applications. Discussion of some relevant experimental techniques (also non-linear) and their application for solving chemical problems, analysis on atmospheric pollutants, and for the studies of surfaces and adsorption processes, orientational analysis of interfacial molecular groups: laser sources, 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). SERS and TERS Techniques. SHG and Sum Frequency Generation – Vibrational Spectroscopy (SFG-VS). SHG and THG microscopies, their coupling with 2PH-AF spectroscopy and their applications in biology and biochemistry.
MAGNETIC SPECTROSCOPIES (NMR and EPR)
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 (Hard and Soft) and pulse shaping in modern FT-NMR spectroscopy. General description of the instrument. Phase correction.
Descriptions of the main Hamiltonians employed for describing NMR spectroscopy. NMR in isotropic and anisotropic medium. Basic concepts on solid-state NMR. Experimental measurements of spin-lattice and spin-spin relaxation processes. Product operator formalism. Population and coherences. In-phase and anti-phase magnetization and their dynamic interconversion. Magnetization transfer through scalar coupling. Applications of the IUPAC guidelines for the representation of pulse sequences for solution-state NMR. Spin-echo pulse sequence and heteronuclear coherence transfer using Insensitive Nuclei Enhanced by Polarization Transfer (INEPT). Description of a general bi-dimensional experiment. Correlation SpectroscopY. Multiple quantum terms. Coherence-order calculation. Evolution of multiple quantum terms. Description of the Double Quantum Filtered COSY (DQF-COSY) experiment. Parameters of the pulse sequences and their product operator analysis for: HETero-nuclear CORrelation spectroscopy (HETCOR), Heteronuclear Multiple Quantum Coherence (HMQC), Heteronuclear Multiple Bond Coherence (HMBC), PGSE, LED/BPLED, DOSY-COSY, MAD, SCALPEL, and PSYCHE. Examples and applications. Presaturation and analysis of pulse sequences WET, WATERGATE, PE-WATERGATE and WASTED. Basic concepts on 3D-NMR and triple-resonance experiments. Basic concepts on solid state NMT.
Electron paramagnetic resonance (epr) spectroscopy. 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 of EPR spectra and of its applications.

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. Besides, additional materials, e.g. scientific articles, during the lectures. After each lecture, the slides employed (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.

STRUCTURE AND CONTENT OF THE COURSE COULD CHANGE AS A RESULT OF THE COVID-19 EPIDEMIC.

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This subject deals with topics related to the macro-area "Climate change and energy" and contributes to the achievement of one or more goals of U. N. Agenda for Sustainable Development