Spectroscopy

After having successfully completed this course, students must be able to:
• Understand and use the concepts related to spectroscopy, the quantum mechanical theory that supports it and the main spectroscopic techniques used in Chemistry.
• Understand the qualitative and quantitative aspects of spectroscopic problems and develop the ability to solve them through numerical and computational techniques.
• Manage spectroscopic instrumentation and interpret data from observations and measurements in the spectroscopy laboratory using quantum mechanics.

Descriptors of the course
The interaction between electromagnetic radiation and matter. Absorption, emission, and Raman scattering spectroscopies. Spin magnetic resonance spectroscopy. Experimental laboratory with special emphasis on the application of spectroscopic techniques to the study of systems of chemical-physical interest.

Contents
1. Introduction to spectroscopy
Introduction. Absorption and emission of radiation. Experimental techniques. Transitions and spectra. Molecular energy levels. Transition moment and selection rules. Intensity of the spectral lines. Population of energy levels: the Boltzmann distribution. The Beer-Lambert law.

2. Molecular vibration. Vibrational absorption and emission spectra
Vibration of diatomic molecules: harmonic and anharmonic oscillator models. Vibrational absorption and emission transitions. Vibrational absorption spectroscopy. Vibration of polyatomic molecules. Vibrational normal modes. Selection rules. Infrared spectra of polyatomic molecules.

3. Molecular rotation. Rotational absorption and emission spectra. Rotational structure of vibrational spectra
Molecular rotors. Moments of inertia and rotational energy levels of linear molecules. Rotational absorption and emission transitions. Microwave spectroscopy. Rovibrational energy levels of diatomic molecules. Rovibrational absorption spectra of diatomic molecules.

4. Vibrational and rotational Raman spectra
Scattering of radiation (Rayleigh and Raman). Raman spectroscopy. Vibrational Raman spectra of diatomic molecules. Vibrational Raman spectra of polyatomic molecules. Rotational Raman spectra of diatomic molecules. Applications of Raman spectroscopy.

5. Electronic transitions
Atomic electronic spectra. Electronic spectra of diatomic molecules. Vibrational structure of electronic spectra. Franck-Condon factors. Electronic spectra of polyatomic molecules. Fluorescence and phosphorescence. Molecules in excited electronic states and photochemistry. Lasers.

6. Magnetic resonance
Energy levels of nuclear and electronic spin in a magnetic field. Magnetic resonance spectroscopy. Nuclear magnetic resonance. The chemical shift. Fine structure of the spectra.

LABORATORY EXPERIMENTS
Experiment 1. Electronic absorption spectra of cyanine dyes. Interpretation using the free electron molecular orbital model and determination of bond distances.
Experiment 2. Infrared and Raman vibrational spectra. Normal vibration modes.
Experiment 3. Fluorescence spectra. Influence of excitation wavelength and determination of vibronic energy levels.

RECOMMENDED TEXTBOOKS
• P. Atkins, J. de Paula and J. Keeler, Physical Chemistry, Oxford University Press, Oxford, 12th ed., 2022.
• C. N. Banwell and E. M. McCash, Fundamentals of Molecular Spectroscopy, McGraw-Hill, London, 4th ed., 1994.
• A. Burrows, J. Holman, et al., Chemistry3: Introducing Inorganic, Organic, and Physical Chemistry, Oxford University Press, Oxford, 4th ed., 2021. A previous edition of this book has a section of resources available openly on the publisher's website, with self-evaluation questionnaires and summaries of each chapter:
https://oup-arc.com/access/burrows3e-student-resources#tag_chapter-10
• Chemistry LibreTexts. University of California Davis. Spectroscopy,
http://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Spec…

COMPLEMENTARY PHYSICAL CHEMISTRY TEXTBOOKS
• H. Kuhn, H.-D. Försterling and D. H. Waldeck, Principles of Physical Chemistry, Wiley, Hoboken, New Jersey, 2nd ed., 2009.
• T. Engel and P. Reid, Physical Chemistry, Pearson, Boston, 3rd ed., 2013.
• G. M. Barrow, Physical Chemistry, McGraw-Hill, New York, 6th ed., 1996.
• K. W. Kolasinski, Physical Chemistry: How chemistry works, John Wiley & Sons, Chichester, 2017.
• M. Díaz Peña and A. Roig Muntaner, Química Física, Alhambra, Madrid, 2nd ed., 1985, Vol. 1.
• G. W. Castellan, Fisicoquímica, Addison Wesley Longman, México, 2nd ed., 1998.
• K. J. Laidler, J. H. Meiser and B. C. Sanctuary, Physical Chemistry, Houghton Mifflin Company, Boston, 4th ed., 2003.

PROBLEM SOLVING BOOKS
• L. Carballeira Ocaña and I. Pérez Juste, Problemas de Espectroscopía Molecular, Netbiblo, Oleiros (Coruña), 2008.
• P. Bolgar et al., Student Solutions Manual to accompany Atkins' Physical Chemistry, Oxford University Press, Oxford, 11th ed., 2018. There are versions of previous editions by other authors.
• J. Bertrán Rusca and J. Núñez Delgado, Problemas de Química Física, Delta, Madrid, 2013.
• I. N. Levine, Problemas de Fisicoquímica, Schaum (McGraw-Hill), Madrid, 2005.
• I. N. Levine, Student Solutions Manual to accompany Physical Chemistry, McGraw-Hill, Boston, 6th ed., 2009.
• J. M. Pérez Martínez, A. L. Esteban Elum and M. P. Galache Payá, Problemas resueltos de Química Cuántica y Espectroscopía Molecular, Univ. de Alicante, Alicante, 2001.

COMPLEMENTARY SPECTROSCOPY TEXTBOOKS
• J. M. Hollas, Basic Atomic and Molecular Spectroscopy, Wiley Interscience & Royal Society of Chemistry, 2002.
• R. Chang, Principios básicos de espectroscopía, Editorial AC, Madrid, 1983.
“Oxford Chemistry Primers”, from Oxford University Press, has several spectroscopy books at introductory level:
• J. M. Brown, Molecular Spectroscopy, 1998.
• S. Duckett and B. Gilbert, Foundations of Spectroscopy, 2000.

GENERAL COMPETENCES
Upon completion of this course students are expected to be able to:
CG2. Gather and interpret data, information and relevant results, establish conclusions and prepare reports on scientific, technological or other issues that require the knowledge of Chemistry.
CG3. Apply theoretical and practical knowledge acquired during the course as well as to face problems and search for their solutions both in academic and professional contexts.
CG4 Have the ability to communicate, both in writing and speaking, knowledge, procedures, results and ideas in chemistry to specialized and non-specialized public.
CG5. Study and learn autonomously, with organization of time and resources, new knowledge and techniques in any scientific or technological discipline.

TRANSVERSAL COMPETENCES
CT1. Acquire capacity of analysis and synthesis.
CT4. Be able to solve problems.

SPECIFIC COMPETENCES
CE13. Be able to demonstrate knowledge and understanding of the essential facts, concepts, principles and theories related to the areas of Chemistry.
CE14. Be able to solve qualitative and quantitative problems according to models developed previously.
CE19. Acquire skill in handling standard chemical instrumentation such as that used for structural investigations and separations.
CE20. Be able to interpret data from observations and measurements in the laboratory in terms of its significance and the theories that support it.

Different types of classes will be taught in this course:

- Large-group lectures
Explanations of the instructor will be combined with the completion of exercises by the students.

- Small-group interactive classes
Practical classes where applications of the theory, problems, exercises, etc., are proposed and solved.

- Tutorials in very small groups
They will be used to foster classroom discussions and to facilitate the students to acquire a general vision of the subject.

- Laboratory practical classes in very small groups
The activities to be carried out in these classes are designed for students to acquire the skills of a Spectroscopy laboratory, including performing spectra, interpreting them according to physicochemical models, and reporting the results and the conclusions in a scientifically rigorous manner. Attendance at these classes is mandatory.

All the teaching material will be available on the virtual learning platform: information on the subject, theory summaries, bulletins of problems, laboratory manual, exams from previous years, etc.

The instructors will attend student queries in the weekly tutoring schedule that is published at the beginning of the course on the University website and on the virtual learning platform.

The assessment system of this subject will be the same for the first and the second opportunities.
The qualification will be carried out through continuous assessment and a final exam. The final grade will not be lower than that of the final exam nor that obtained by averaging it with the continuous assessment, giving a weight of 40% to the latter. To pass the course, it is required to obtain a pass mark in the laboratory work.

The final exam will include theoretical and conceptual questions (4 points), problems (4 points) and questions related to laboratory practices (2 points).

In the continuous assessment, the student's personal work throughout the course will be assessed by exercises and questionnaires (80%) and by activities carried out in the laboratory (20%).

To obtain the pass qualification in the laboratory work, it is required to:
• Attend all the programmed practices. Students who cannot attend the laboratory practices on schedule, for justified reasons, will have to perform them in a different schedule, in agreement with the instructors and the programmed timetable of the course.
• Carry out the practices correctly and upload on the virtual learning platform the requested analysis documents within the required period.

The laboratory exercises are not mandatory for students who obtained a pass qualification in one of the two immediately preceding courses (i.e., the laboratory mark may be kept for two consecutive years). They will also be able to improve the mark by taking the practical exam.

In cases of fraudulent performance of exercises or tests, the provisions of the "Normativa de evaluación del rendimiento académico de los estudiantes y de revisión de calificaciones" of the USC will apply.

Throughout the course the following competences are assessed:
Interactive lectures: CG2, CG3, CG4, CG5, CT1, CT4, CE13, CE14
Laboratory classes: CG2, CG3, CG4, CT1, CT4, CE19, CE20
Tutorials: CG4, CG5, CT1, CE13
Final exam: CG2, CG3, CG4, CG5, CT1, CT4, CE13, CE14, CE20

Classes in a large group: 28 hours
Interactive classes in a small group: 13 hours
Laboratory classes: 17 hours
Tutorials in a small group: 2 hours
Total hours of face-to-face work in classroom or laboratory: 60 hours
Autonomous student work: 90 hours
Total work hours: 150

RECOMMENDATIONS FOR THE STUDY

• The laboratory experiments of this subject are directly related to the theory, so it is advisable to review the theory before accessing the laboratory in order to understand the experiments. Without an adequate knowledge of the theory it is very difficult to understand the tasks to be carried out in the lab, which have a high component of spectroscopic data analysis.

• It is important to keep up to date in assignments.

• Once the reading of a topic in the reference manual is finished, it is useful to summarize the important points, identifying the basic equations and making sure you know both their meaning and the conditions under which they can be applied.

• Problem solving is fundamental for learning this subject. It may be helpful to follow these steps: (1) make a list of all the relevant information provided by the problem statement, (2) make a list of the quantities to be calculated and, if possible, a scheme of the relevant data and information sought and (3) identify the equations to be used in solving the problem and apply them correctly. These and other recommendations for the study of Physical Chemistry and for the resolution of problems are included in sections 1.9 (chapter 1) and 2.12 (chapter 2) of the book "Physical Chemistry" of I. N. Levine.

RECOMMENDATIONS FOR THE ASSESSMENT
It is recommended that those students who find significant difficulties to solve the proposed activities consult with the instructors in the hours of individual tutoring, to analyse the problems and try to solve them.

RECOMMENDED PREREQUISITES
It is very important to have passed the course on Quantum Chemistry, since the concepts of Spectroscopy are directly related to that subject. It is also advisable to have passed the Mathematics I and II, Physics I and II, Applied Statistics and Computer Science for Chemists and General Chemistry I and II.