9 ECTS credits
270 h study time

Offer 1 with catalog number 4023200ENR for all students in the 1st semester at a (E) Master - advanced level.

Semester
1st semester
Enrollment based on exam contract
Impossible
Grading method
Grading (scale from 0 to 20)
Can retake in second session
Yes
Enrollment Requirements
Students must have followed 'Introduction to Quantum Chemistry’ and 'Physical Chemistry : Quantum Chemistry', before they can enroll for ‘Molecular Physical Chemistry'.
Taught in
English
Faculty
Faculty of Sciences and Bioengineering Sciences
Department
Chemistry
Educational team
Paul Geerlings
Frank De Proft (course titular)
Activities and contact hours
52 contact hours Lecture
39 contact hours Seminar, Exercises or Practicals
Course Content

Part 1: From atomic/molecular energy levels to spectral transitions 

 

1.1. Basic notions of spectrosopy (recapitulation)) 

1.2. Atomic Spectroscopy 

  • Selection Rules for the Hydrogen Atom 

  • Energy-levels for multi-electron-atoms: influence of correlation and relativistic effects. 

  • Spectral transitions and selection rules. 

1.3. Molecular Spectroscopy: basic principles and partitioning of the molecular energy 

1.4. Vibrational energy-levels and selection rules 

  • Diatomic molecules: the harmonic model and anharmonicity corrections 

  • Polyatomic Molecules: IR and Raman spectroscopy. 

1.5. Rotational Spectroscopy 

  • Rotational energy-levels and selection-rules. 

1.6. Electronic Spectra (unsaturated systems) 

  • Huckel’s method for unsaturated systems 

  • Applications 

  • Electronic Transitions in the MO model 

1.7. Electron and nuclear spin resonance 

  • The e.s.r. experiment 

  • The NMR experiment 

 

Part 2 From energy-levels to macroscopic thermodynamic behaviour 

 

2.1. Basic principles of Statistical Mechanics: non-interacting molecules 

  • Boltzmann distribution 

  • Partition function 

  • Internal energy 

2.2. Some applications of non-interacting molecules 

  • Factorisation of the partition function 

  • Thermodynamic properties of ideal gases 

  • Equipartition theorem 

  • Partition functions for internal degrees of freedom (rotations, vibrations, electronic) 

2.3. Canonical ensemble and indistinguishability 

  • From the Canonical ensemble to thermodynamic functions 

  • The Sackur-Tetrode equation for the entropy of atoms. 

  • Equilibrium constants for ideal gases. 

 

Modelling skills 

 

1. Practical introduction to electronic structure methods with particular attention for density functional theory  

2. Computation of the electronic structure and interpretation of the results 

3. Geometry optimization: minima and saddle points (transition states)  

4. Computation of spectroscopic quantities: electronic transitions, vibrational frequencies and NMR properties  

5. ab initio molecular dynamics: dynamic properties and solvent effects 

Additional info

Course material: 

  • Course (Recommended): Molecular Physical chemistry, P. Geerlings – F. De Proft, VUB, 2220170000725, 2016. 

  • Molecular Quantum Mechanics, P. W. Atkins and R. S. Friedman, Fifth Edition, Oxford University Press, Oxford, 2010. 

  • Matter in Equilibrium, Statistical Mechanics and Thermodynamics, R. S. Berry, S. A. Rice and J. Ross, Second Edition, 2002. 

  • Physical Chemistry, P. W. Atkins and J. De Paula, 11th Edition, Oxford University Press, Oxford, 2017. 

Learning Outcomes

general competencies

The aim of the first part of this course is, starting from the energy-levels of atoms and molecules, obtained through Quantum Mechanics/Quantum Chemistry, to give insight into their fundamental role in the interpretation of atomic and molecular (rotational, vibrational, electronic) spectra. This part thereby gives further theoretical support to the course on structure determination in the Bachelor courses. 

The second part shows how these same energy-levels give access, in a statistical-mechanical context, via the partition function, to the classical thermodynamical state functions (energy, free energy, entropy, ...) and how finally equilibrium constants of chemical reactions can be evaluated. In this sense a link is drawn to the course on Thermodynamics in the Bachelor curriculum. 

 

For the modelling part of the course, the specific learning outcomes are: 

  • Students can model optical and electronic properties of molecules through density functional theory. 

  • Students can independently perform state-of-the-art density functional calculations of different properties and can correctly interpret the results 

Grading

The final grade is composed based on the following categories:
Other Exam determines 100% of the final mark.

Within the Other Exam category, the following assignments need to be completed:

  • written+oral+assignment with a relative weight of 100 which comprises 100% of the final mark.

Additional info regarding evaluation

80 % of the mark is given on the exam, which is composed of a written part (Problems - Open book) followed by an oral exam with written preparation (theory, closed book). This combination permits to assess physical and chemical insight, computational skill, and strength in analysis and synthesis.

20 % of the mark is given on an assignment on the molecular modelling part of the WPO 

Allowed unsatisfactory mark
The supplementary Teaching and Examination Regulations of your faculty stipulate whether an allowed unsatisfactory mark for this programme unit is permitted.

Academic context

This offer is part of the following study plans:
Master of Chemistry: Analytical and Environmental Chemistry
Master of Chemistry: Chemical Theory, (Bio)Molecular Design and Synthesis
Master of Teaching in Science and Technology: chemie (120 ECTS, Etterbeek) (only offered in Dutch)