Module 1: Energy levels of atoms and molecules#
This module introduces some fundamental concepts in quantum mechanics focusing on the different quantized energy levels in atoms and molecules.
Rather than a systematic development of Quantum theory it covers the analytical simple systems that can later on explain translational, electronic, vibrational, and rotational levels that are needed for statistical thermodynamics in the next module.
A note for those who learned quantum mechanics elsewhere: we will focus on the results of quantum theory applied to atomic and molecular systems rather than the mathematical development. For example, there is no mention of the Hilbert space, the orthogonalization of a base, commuting operators, wavefunction conjugates…etc
The sections in this chapter are:
Bohr’s hydrogen atom
Experimental series
Bohr’s hydrogen model
Calculating wavelengths of the Lymann series
Introduction to Quantum Mechanics. Particle in a box.
The Schrodinger equation for a particle in a box
The quantized energy of the particle
The effect of mass and size of the box. Zero point energy
The wavefunctions of the particle in a box and their meaning
Particle in a box in 2D and 3D. Degeneracy. Plotting 2D wavefunctions
Schrodinger’s hydrogen atom
The Hamiltonian for the hydrogen atom
Solutions to the Schrodinger equation for hydrogen: the orbitals
Energy levels of hydrogen
The radial solution: the size of the atom
Plotting the entire wavefunction: probability and cutoff
Polyelectronic atoms. Electronic correlation and self-consistent field methods
The Hamiltonian for polyelectronic atoms
The Self-Consistent Field solution (SCF) or Hartree-Fock
Quantum chemistry packages: pyscf
Single point calculations. Reading the output
Testing basis sets
Different levels of theory
Ionization energy of atoms
Electronic energy of molecules
The Born-Oppenheimer approximation and potential energy surface
Single point energy of molecules. Assessing the energy of different spin states.
Population analysis
Scanning a distance to find a bond distance
Homolytic and heterolytic breaking of a bond
Structure optimization: optimizing the geometry of water
Vibrational levels of diatomic molecules
The Schrodinger Equation of Nuclear Motion
The harmonic approximation to nuclear motion: The harmonic oscillator
Using the classical harmonic oscillator to assess the “quantumness” of the system
Infrared spectroscopy
Anharmonic corrections
Vibrational levels of polyatomic molecules
Normal modes of vibration
Rotational levels of molecules
The Schrodinger equation for nuclear coordinates: the polar coordinates of the nuclear motion show rotation
The rigid rotor approximation: energy rotational levels and energy spacing: Effect of mass and bond distance
Degeneracy of the rigid rotor
Microwave spectroscopy