1 Advanced Chemical Physics

2 Advanced Physical Chemistry Spectroscopy –Electronic spectroscopy (basics in quantum mechanics) –Vibrational spectroscopy (IR+Raman) –Time resolved spectroscopy –Surface spectroscopy –Single molecule spectroscopy –Photoelectrons spectroscopy Advanced Topics in Thermodynamics and Kinetics –Liquid-solid interfaces (wetting, contact angle) –Molecules at Interfaces (Langmuir films, self-assembled layers) –Catalysis (Chemisorption, kinetics, mechanisms) –Structure and dynamics in liquids Books: 1. Modern Spectroscopy, J. M. Hollas, John Wiley&Sons 2. Molecular Vibrations, Wilson, Decious and Cross, Dover Publications Inc. 3. Physical Chemistry of Surfaces, A.W. Adamson and Cast, Wiley- Interscience Publication. 4. “An Introduction to the Liquid State" by P.A. Egelstaff, Oxford University Press.

3 Electronic Spectroscopy Quantum mechanics- Born-Oppenheimer approximation Molecular symmetry Electromagnetic radiation and its interaction with atoms and molecules Coupling of angular momenta Classification of electronic states and selection rules. Vibronic spectra, Franck-Condon principle and selection rules Non Born-Oppenheimer effects, radiationless transitions.

4 Quantum mechanics- Born-Oppenheimer approximation In 1924 Louis de Broglie recognized the similarity that exists between Fermat’s principle of least time, which governed the propagation of light, and Maupertuis’s principle of least action, which governed the propagation of particles. He proposed that with any moving body there is associated a wave and that the momentum of the particle and the wavelength are related by: p=h/. It can be shown that as a result of this relation one obtains also the Heisenberg uncertainty principle:  p  x ≥h. Hence in order that an electron will reside in a radius around a nuclei a standing wave must exist in which

5 In quantum mechanics we deal with the solution of the Schrödinger Equation, which is an equation for the spatial and temporal behavior of the de Broglie waves: The Schrödinger Equation is given by:

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11 Molecular Symmetry

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13 Electromagnetic radiation and its interaction with atoms and molecules

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20 Short Summary The “dream” of any quantum chemist is to present the hamiltonian in the form of: H=h 1 +h 2 + h 3 +…. When h i is hydrogen atom like hamiltonian. The solution is given than as: E=E 1 +E 2 +E 3 +… Alternatively one tries to write the hamiltonian as sum of hamiltonians with the terms that couple them as “off-diagonal” terms.

21 Short Summary-continue The transition dipole moment Because of symmetry considerations the function in the integral must be symmetric. Since the dipole moment is always anti-symmetric, in order that a dipole transition will be “ allowed ”, one of the wave functions must be symmetric and the other anti-symmetric.

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26 Coupling of angular momenta

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32 Classification of electronic states and selection rules.

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40 Selection rules

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