# Table of Contents

- Page ID
- 182379

This is the textmap for the Physical chemistry textbook by McQuarrie and Simon.

## 1: The Dawn of the Quantum Theory

"With the recognition that there is no logical reason why Newtonian and classical principles should be valid outside the domains in which they have been experimentally verified has come the realization that departures from these principles are indeed necessary. Such departures find their expression through the introduction of new mathematical formalisms, new schemes of axioms and rules of manipulation, into the methods of theoretical physics." - P. A. M. Dirac,## 2: The Classical Wave Equation

The aim of this section is to give a fairly brief review of waves in various shaped elastic media—beginning with a taut string, then going on to an elastic sheet, a drumhead, first of rectangular shape then circular, and finally considering elastic waves on a spherical surface, like a balloon.## 3: The Schrödinger Equation and a Particle in a Box

The particle in a box model provides one of the very few problems in quantum mechanics which can be solved analytically, without approximations. This means that the observable properties of the particle (such as its energy and position) are related to the mass of the particle and the width of the well by simple mathematical expressions. Due to its simplicity, the model allows insight into quantum effects without the need for complicated mathematics.## 4: Postulates and Principles of Quantum Mechanics

Quantum Mechanics is a framework for the development of physical theories. Quantum mechanics is based on a series of postulates which lead to a very good description of the microphysical realm.## 5: The Harmonic Oscillator and the Rigid Rotor

The harmonic oscillator is common: It appears in many everyday examples. The harmonic oscillator is intuitive: We can picture the forces on systems such as pendulum or a plucked string. This makes it simple to study in the classroom. ​​​​​​ The harmonic oscillator is mathematically simple: In studying simple harmonic motion, students can immediately use the formulas that describe its motion.## 6: The Hydrogen Atom

The solution of the Schrödinger equation for the hydrogen atom uses the fact that the Coulomb potential produced by the nucleus is isotropic (it is radially symmetric in space and only depends on the distance to the nucleus). Although the resulting energy eigenfunctions are not necessarily isotropic themselves, their dependence on the angular coordinates follows completely generally from this isotropy of the underlying potential.## 7: Approximation Methods

The Schrödinger equation for realistic systems quickly becomes unwieldy, and analytical solutions are only available for very simple systems - the ones we have described as fundamental systems in this module. Numerical approaches can cope with more complex problems, but are still (and will remain for a good while) limited by the available computer power. Approximations are necessary to cope with real systems.## 8: Multielectron Atoms

Electrons with more than one atom, such as Helium (He), and Nitrogen (N), are referred to as multi-electron atoms. Hydrogen is the only atom in the periodic table that has one electron in the orbitals under ground state. We will learn how additional electrons behave and affect a certain atom.## 9: Chemical Bonding in Diatomic Molecules

Our basis for understanding chemical bonding and the structures of molecules is the electron orbital description of the structure and valence of atoms, as provided by quantum mechanics. We assume an understanding of the periodicity of the elements based on the nuclear structure of the atom and our deductions concerning valence based on electron orbitals.## 10: Bonding in Polyatomic Molecules

The concept of a molecular orbital is readily extended to provide a description of the electronic structure of a polyatomic molecule. In general a molecular orbital in a polyatomic system extends over all the nuclei in a molecule and it is essential, if we are to understand and predict the spatial properties of the orbitals, that we make use of the symmetry properties possessed by the nuclear framework.## 11: Computational Quantum Chemistry

Quantum chemistry addresses the equations and approximations derived from the postulates of quantum mechanics; specifically involving solving the Schrödinger equation for molecular systems and is typically separated into ab initio, which uses methods that do not include any empirical parameters or experimental data and semi-empirical that do.## 12: Group Theory - The Exploitation of Symmetry

One important application, the theory of symmetry groups, is a powerful tool for the prediction of physical properties of molecules and crystals. It is for example possible to determine whether a molecule can have a dipole moment. Many important predictions of spectroscopic experiments (optical, IR or Raman) can be made purely by group theoretical considerations.## 13: Molecular Spectroscopy

Spectroscopy generally is defined as the area of science concerned with the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules. Visible electromagnetic radiation is called light, although the terms light, radiation, and electromagnetic radiation can be used interchangeably. Spectroscopy played a key role in the development of quantum mechanics and is essential to understanding molecular properties and the results of spectroscopic experiments.## 17: Boltzmann Factor and Partition Functions

Statistical Mechanics provides the connection between microscopic motion of individual atoms of matter and macroscopically observable properties such as temperature, pressure, entropy, free energy, heat capacity, chemical potential, viscosity, spectra, reaction rates, etc. Statistical Mechanics provides the microscopic basis for thermodynamics, which, otherwise, is just a phenomenological theory.## 26: Chemical Equilibrium

The natural tendency of chemical systems is to seek a state of minimum Gibbs function. Once the minimum is achieved, movement in any chemical direction will not be spontaneous. It is at this point that the system achieves a state of equilibrium.## 27: The Kinetic Theory of Gases

The Maxwell-Boltzmann distribution is used to determine how many molecules are moving between velocities.## 28: Chemical Kinetics I - Rate Laws

In general, increases in temperature increase the rates of chemical reactions. It is easy to see why, since most chemical reactions depend on molecular collisions. Since the frequency with which molecules collide increases with increased temperature. But also, the kinetic energy of the molecules increases, which should increase the probability that a collision event will lead to a reaction. An empirical model was proposed by Arrhenius to account for this phenomenon.## 29: Chemical Kinetics II: Reaction Mechanisms

In this chapter, we will expand on the concepts of chemical reaction rates by exploring what the rate law implies about the mechanistic pathways that reactions actually follow to proceed from reactants to products. Typically, one determines a rate law that describes a chemical reaction, and then suggests a mechanism that can be (or might not be!) consistent with the observed kinetics.