Map: Physical Chemistry (McQuarrie and Simon)
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- 1: The Dawn of the Quantum Theory
- 1.1: Blackbody Radiation Cannot Be Explained Classically
- 1.2: Quantum Hypothesis Used for Blackbody Radiation Law
- 1.3: Photoelectric Effect Explained with Quantum Hypothesis
- 1.4: The Hydrogen Atomic Spectrum
- 1.5: The Rydberg Formula and the Hydrogen Atomic Spectrum
- 1.6: Matter Has Wavelike Properties
- 1.7: de Broglie Waves can be Experimentally Observed
- 1.8: The Bohr Theory of the Hydrogen Atom
- 1.9: The Heisenberg Uncertainty Principle
- 1.E: The Dawn of the Quantum Theory (Exercises)
- 2: The Classical Wave Equation
- 3: The Schrödinger Equation and a Particle in a Box
- 3.1: The Schrödinger Equation
- 3.2: Linear Operators in Quantum Mechanics
- 3.3: The Schrödinger Equation is an Eigenvalue Problem
- 3.4: Wavefunctions Have a Probabilistic Interpretation
- 3.5: The Energy of a Particle in a Box is Quantized
- 3.6: Wavefunctions Must Be Normalized
- 3.7: The Average Momentum of a Particle in a Box is Zero
- 3.8: The Uncertainty Principle - Estimating Uncertainties from Wavefunctions
- 3.9: A Particle in a Three-Dimensional Box
- 3.E: The Schrödinger Equation and a Particle in a Box (Exercises)
- 4: Postulates and Principles of Quantum Mechanics
- 4.1: The Wavefunction Specifies the State of a System
- 4.2: Quantum Operators Represent Classical Variables
- 4.3: Observable Quantities Must Be Eigenvalues of Quantum Mechanical Operators
- 4.4: The Time-Dependent Schrödinger Equation
- 4.5: Eigenfunctions of Operators are Orthogonal
- 4.6: Commuting Operators Allow Infinite Precision
- 4.E: Postulates and Principles of Quantum Mechanics (Exercises)
- 5: The Harmonic Oscillator and the Rigid Rotor
- 5.1: A Harmonic Oscillator Obeys Hooke's Law
- 5.2: The Equation for a Harmonic-Oscillator Model of a Diatomic Molecule Contains the Reduced Mass of the Molecule
- 5.3: The Harmonic Oscillator Approximates Vibrations
- 5.4: The Harmonic Oscillator Energy Levels
- 5.5: The Harmonic Oscillator and Infrared Spectra
- 5.6: The Harmonic-Oscillator Wavefunctions Involve Hermite Polynomials
- 5.7: Hermite Polynomials are either Even or Odd Functions
- 5.8: The Energy Levels of a Rigid Rotor
- 5.9: The Rigid Rotator is a Model for a Rotating Diatomic Molecule
- 5.E: The Harmonic Oscillator and the Rigid Rotor (Exercises)
- 6: The Hydrogen Atom
- 6.1: The Schrodinger Equation for the Hydrogen Atom Can Be Solved Exactly
- 6.2: The Wavefunctions of a Rigid Rotator are Called Spherical Harmonics
- 6.3: The Three Components of Angular Momentum Cannot be Measured Simultaneously with Arbitrary Precision
- 6.4: Hydrogen Atomic Orbitals Depend upon Three Quantum Numbers
- 6.5: s Orbitals are Spherically Symmetric
- 6.6: Orbital Angular Momentum and the p-Orbitals
- 6.7: The Helium Atom Cannot Be Solved Exactly
- 6.E: The Hydrogen Atom (Exercises)
- 7: Approximation Methods
- 7.1: The Variational Method Approximation
- 7.2: Linear Variational Method and the Secular Determinant
- 7.3: Trial Functions Can Be Linear Combinations of Functions That Also Contain Variational Parameters
- 7.4: Perturbation Theory Expresses the Solutions in Terms of Solved Problems
- 7.E: Approximation Methods (Exercises)
- 8: Multielectron Atoms
- 8.1: Atomic and Molecular Calculations are Expressed in Atomic Units
- 8.2: Perturbation Theory and the Variational Method for Helium
- 8.3: Hartree-Fock Equations are Solved by the Self-Consistent Field Method
- 8.4: An Electron Has an Intrinsic Spin Angular Momentum
- 8.5: Wavefunctions must be Antisymmetric to Interchange of any Two Electrons
- 8.6: Antisymmetric Wavefunctions can be Represented by Slater Determinants
- 8.7: Hartree-Fock Calculations Give Good Agreement with Experimental Data
- 8.8: A Term Symbol Gives a Detailed Description of an Electron Configuration
- 8.9: The Allowed Values of J - the Total Angular Momentum Quantum Number
- 8.10: Hund's Rules Determine the Term Symbols of the Ground Electronic States
- 8.11: Using Atomic Term Symbols to Describe Atomic Spectra
- 8.E: Multielectron Atoms (Exercises)
- 9: Chemical Bonding in Diatomic Molecules
- 9.1: The Born-Oppenheimer Approximation Simplifies the Schrödinger Equation for Molecules
- 9.2: The H₂⁺ Prototypical Species
- 9.3: The Overlap Integral
- 9.4: Chemical Bond Stability
- 9.5: Bonding and Antibonding Orbitals
- 9.6: A Simple Molecular-Orbital Treatment of H₂ Places Both Electrons in a Bonding Orbital
- 9.7: Molecular Orbitals Can Be Ordered According to Their Energies
- 9.8: Molecular-Orbital Theory Does not Predict a Stable Diatomic Helium Molecule
- 9.9: Electrons Populate Molecular Orbitals According to the Pauli Exclusion Principle
- 9.10: Molecular Orbital Theory Predicts that Molecular Oxygen is Paramagnetic
- 9.11: Photoelectron Spectra Support the Existence of Molecular Orbitals
- 9.12: Molecular-Orbital Theory Also Applies to Heteronuclear Diatomic Molecules
- 9.13: An SCF-LCAO-MO Wave Function Is a Molecular Orbital Formed from a Linear Combination of Atomic Orbitals and Whose Coefficients Are Determined Self-Consistently
- 9.14: Molecular Term Symbols Describe Electronic States of Molecules
- 9.15: Molecular Term Symbols Designate Symmetry
- 9.16: Most Molecules Have Excited Electronic States
- 9.E: Chemical Bond in Diatomic Molecules (Exercises)
- 10: Bonding in Polyatomic Molecules
- 10.1: Hybrid Orbitals Account for Molecular Shape
- 10.2: Hybrid Orbitals in Water
- 10.3: Why is BeH₂ Linear and H₂O Bent?
- 10.4: Photoelectron Spectroscopy
- 10.5: The \(\pi\)-Electron Approximation of Conjugation
- 10.6: Butadiene is Stabilized by a Delocalization Energy
- 10.7: Benzene and Aromaticity
- 10.E: Bonding in Polyatomic Molecules (Exercises)
- 11: Computational Quantum Chemistry
- 12: Group Theory - The Exploitation of Symmetry
- 12.1: The Exploitation of Symmetry
- 12.2: Symmetry Elements
- 12.3: Symmetry Operations Define Groups
- 12.4: Symmetry Operations as Matrices
- 12.5: The \(C_{3V}\) Point Group
- 12.6: Character Tables
- 12.7: Characters of Irreducible Representations
- 12.8: Using Symmetry to Solve Secular Determinants
- 12.9: Generating Operators
- 12.E: Group Theory - The Exploitation of Symmetry (Exercises)
- 13: Molecular Spectroscopy
- 13.1: The Electromagnetic Spectrum
- 13.2: Rotations Accompany Vibrational Transitions
- 13.3: Unequal Spacings in Vibration-Rotation Spectra
- 13.4: Unequal Spacings in Pure Rotational Spectra
- 13.5: Vibrational Overtones
- 13.6: Electronic Spectra Contain Electronic, Vibrational, and Rotational Information
- 13.7: The Franck-Condon Principle
- 13.8: Rotational Spectra of Polyatomic Molecules
- 13.9: Normal Modes in Polyatomic Molecules
- 13.10: Irreducible Representation of Point Groups
- 13.11: Time-Dependent Perturbation Theory
- 13.12: The Selection Rule for the Rigid Rotor
- 13.13: The Harmonic Oscillator Selection Rule
- 13.14: Group Theory Determines Infrared Activity
- 13.E: Molecular Spectroscopy (Exercises)
- 14: Nuclear Magnetic Resonance Spectroscopy
- 14.1: Nuclei Have Intrinsic Spin Angular Momenta
- 14.2: Magnetic Moments Interact with Magnetic Fields
- 14.3: Proton NMR Spectrometers Operate at Frequencies Between 60 MHz and 750 MHz
- 14.4: The Magnetic Field Acting upon Nuclei in Molecules Is Shielded
- 14.5: Chemical Shifts Depend upon the Chemical Environment of the Nucleus
- 14.6: Spin-Spin Coupling Can Lead to Multiplets in NMR Spectra
- 14.7: Spin-Spin Coupling Between Chemically Equivalent Protons is Not Observed
- 14.8: The n+1 Rule Applies Only to First-Order Spectra
- 14.9: Second-Order Spectra Can Be Calculated Exactly Using the Variational Method
- 14.E: Nuclear Magnetic Resonance Spectroscopy (Exercises)
- 15: Lasers, Laser Spectroscopy, and Photochemistry
- 15.1: Electronically Excited Molecules can Relax by a Number of Processes
- 15.2: The Dynamics of Transitions can be Modeled by Rate Equations
- 15.3: A Two-Level System Cannot Achieve a Population Inversion
- 15.4: Population Inversion can be Achieved in a Three-Level System
- 15.5: What is Inside a Laser?
- 15.6: The Helium-Neon Laser
- 15.7: High-Resolution Laser Spectroscopy
- 15.8: Pulsed Lasers Can by Used to Measure the Dynamics of Photochemical Processes
- 15.E: Lasers, Laser Spectroscopy, and Photochemistry (Exercises)
- 16: The Properties of Gases
- 16.1: All Dilute Gases Behave Ideally
- 16.2: van der Waals and Redlich-Kwong Equations of State
- 16.3: A Cubic Equation of State
- 16.4: The Law of Corresponding States
- 16.5: The Second Virial Coefficient
- 16.6: The Repulsive Term in the Lennard-Jones Potential
- 16.7: Van der Waals Constants in Terms of Molecular Parameters
- 16.E: The Properties of Gases (Exercises)
- 17: Boltzmann Factor and Partition Functions
- 17.1: The Boltzmann Factor
- 17.2: The Thermal Boltzman Distribution
- 17.3: The Average Ensemble Energy
- 17.4: Heat Capacity at Constant Volume
- 17.5: Pressure in Terms of Partition Functions
- 17.6: Partition Functions of Distinguishable Molecules
- 17.7: Partition Functions of Indistinguishable Molecules
- 17.8: Partition Functions can be Decomposed
- 17.E: Boltzmann Factor and Partition Functions (Exercises)
- 18: Partition Functions and Ideal Gases
- 18.1: Translational Partition Functions of Monotonic Gases
- 18.2: Most Atoms are in the Ground Electronic State
- 18.3: The Energy of a Diatomic Molecule Can Be Approximated as a Sum of Separate Terms
- 18.4: Most Molecules are in the Ground Vibrational State
- 18.5: Most Molecules are Rotationally Excited at Ordinary Temperatures
- 18.6: Rotational Partition Functions of Diatomic Gases
- 18.7: Vibrational Partition Functions of Polyatomic Molecules
- 18.8: Rotational Partition Functions of Polyatomic Molecules
- 18.9: Molar Heat Capacities
- 18.E: Partition Functions and Ideal Gases (Exercises)
- Ortho and Para Hydrogen
- The Equipartition Principle
- 19: The First Law of Thermodynamics
- 19.0: Overview of Classical Thermodynamics
- 19.1: Pressure-Volume Work
- 19.2: Work and Heat are not State Functions, but Energy is a State Function
- 19.3: Energy is a State Function
- 19.4: An Adiabatic Process is a Process in which No Energy as Heat is Transferred
- 19.5: The Temperature of a Gas Decreases in a Reversible Adiabatic Expansion
- 19.6: Work and Heat Have a Simple Molecular Interpretation
- 19.7: Pressure-Volume Work
- 19.8: Heat Capacity is a Path Function
- 19.9: Relative Enthalpies Can Be Determined from Heat Capacity Data and Heats of Transition
- 19.10: Enthalpy Changes for Chemical Equations are Additive
- 19.11: Heats of Reactions Can Be Calculated from Tabulated Heats of Formation
- 19.12: The Temperature Dependence of ΔH
- 19.E: The First Law of Thermodynamics (Exercises)
- 20: Entropy and The Second Law of Thermodynamics
- 20.1: Energy Does not Determine Spontaneity
- 20.2: Nonequilibrium Isolated Systems Evolve in a Direction That Increases Their Probability
- 20.3: Unlike heat, Entropy Is a State Function
- 20.4: The Second Law of Thermodynamics
- 20.5: The Famous Equation of Statistical Thermodynamics
- 20.6: We Must Always Devise a Reversible Process to Calculate Entropy Changes
- 20.7: Thermodynamics Provides Insight into the Conversion of Heat into Work
- 20.8: Entropy Can Be Expressed in Terms of a Partition Function
- 20.9: The Molecular Formula S = kB in W is Analogous to the Thermodynamic Formula dS = deltaqrev
- 20.E: Entropy and The Second Law of Thermodynamics (Exercises)
- 21: Entropy & the Third Law of Thermodynamics
- 21.1: Entropy Increases With Increasing Temperature
- 21.2: Absolute Entropy
- 21.3: Temperatures at a Phase Transition
- 21.4: The Third Law of Thermodynamics
- 21.5: Practical Absolute Entropies Can Be Determined Calorimetrically
- 21.6: Practical Absolute Entropies of Gases Can Be Calculated from Partition Functions
- 21.7: Standard Entropies Depend Upon Molecular Mass and Structure
- 21.8: Spectroscopic Entropies sometimes disgree with Calorimetric Entropies
- 21.9: Standard Entropies Can Be Used to Calculate Entropy Changes of Chemical Reactions
- 21.E: Entropy & the Third Law of Thermodynamics (Exercises)
- 22: Helmholtz and Gibbs Energies
- 22.1: Helmholtz Energy
- 22.2: Gibbs Energy
- 22.3: The Maxwell Relations
- 22.4: The Enthalpy of an Ideal Gas
- 22.5: Thermodynamic Functions have Natural Variables
- 22.6: The Standard State for a Gas is Ideal Gas
- 22.7: The Gibbs-Helmholtz Equation
- 22.8: Fugacity Measures Nonideality of a Gas
- 22.E: Helmholtz and Gibbs Energies (Exercises)
- 23: Phase Equilibria
- 23.1: A Phase Diagram Summarizes the Solid-Liquid-Gas Behavior of a Substance
- 23.2: Gibbs Energies and Phase Diagrams
- 23.3: The Chemical Potentials of a Pure Substance in Two Phases in Equilibrium
- 23.4: The Clausius-Clapeyron Equation
- 23.5: Chemical Potential Can be Evaluated From a Partition Function
- 23.E: Phase Equilibria (Exercises)
- 24: Solutions I: Liquid-Liquid Solutions
- 24.1: Partial Molar Quantities in Solutions
- 24.2: The Gibbs-Duhem Equation
- 24.3: Chemical Potential of Each Component Has the Same Value in Each Phase in Which the Component Appears
- 24.4: Ideal Solutions obey Raoult's Law
- 24.5: Most Solutions are Not Ideal
- 24.6: Vapor Pressures of Volatile Binary Solutions
- 24.7: Activities of Nonideal Solutions
- 24.8: Activities are Calculated with Respect to Standard States
- 24.9: Gibbs Energy of Mixing of Binary Solutions in Terms of the Activity Coefficient
- 24.E: Solutions I: Liquid-Liquid Solutions (Exercises)
- 25. Solutions II - Solid-Liquid Solutions
- 25.1: Raoult's and Henry's Laws Define Standard States
- 25.2: The Activities of Nonvolatile Solutes
- 25.3: Colligative Properties Depend only on Number Density
- 25.4: Osmotic Pressure can Determine Molecular Masses
- 25.5: Electrolytes Solutions are Nonideal at Low Concentrations
- 25.6: The Debye-Hückel Theory
- 25.7: Extending Debye-Hückel Theory to Higher Concentrations
- Homework Problems
- 26: Chemical Equilibrium
- 26.1: Equilibrium Results when Gibbs Energy is Minimized
- 26.2: An Equilibrium Constant is a Function of Temperature Only
- 26.3: Standard Gibbs Energies of Formation Can Be Used to Calculate Equilibrium Constants
- 26.4: A Plot of the Gibbs Energy of a Reaction Mixture Against the Extent of Reaction Is a Minimum at Equilibrium
- 26.5: Reaction Quotient and Equilibrium Constant Ratio Determines Reaction Direction
- 26.6: The Sign of ΔG and not ΔG° Determines the Direction of Reaction Spontaneity
- 26.7: The Van't Hoff Equation
- 26.8: Equilibrium Constants in Terms of Partition Functions
- 26.9: Molecular Partition Functions and Related Thermodynamic Data Are Extensively Tabulated
- 26.10: Real Gases Are Expressed in Terms of Partial Fugacities
- 26.11: Thermodynamic Equilibrium Constants Are Expressed in Terms of Activities
- 26.12: Activities are Important for Ionic Species
- Homework Problems
- 27: The Kinetic Theory of Gases
- 27.1: The Average Translational Kinetic Energy of a Gas
- 27.2: The Distribution of the Components of Molecular Speeds are Described by a Gaussian Distribution
- 27.3: The Distribution of Molecular Speeds Is Given by the Maxwell-Boltzmann Distribution
- 27.4: The Frequency of Collisions
- 27.5: The Maxwell-Boltzmann Distribution Has Been Verified Experimentally
- 27.6: The Mean Free Path
- 27.7: The Rate of a Gas-Phase Chemical Reactions
- 27.E: The Kinetic Theory of Gases (Exercises)
- 28: Chemical Kinetics I - Rate Laws
- 28.1: The Time Dependence of a Chemical Reaction Is Described by a Rate Law
- 28.2: Rate Laws Must Be Determined Experimentally
- 28.3: First-Order Reactions Show an Exponential Decay of Reactant Concentration with Time
- 28.4: Different Rate Laws Predict Different Kinetics
- 28.5: Reactions Can Also Be Reversible
- 28.6: The Rate Constants of a Reversible Reaction Can Be Determined Using Relaxation Techniques
- 28.7: Rate Constants Are Usually Strongly Temperature Dependent
- 28.8: Transition-State Theory Can Be Used to Estimate Reaction Rate Constants
- 28.E: Chemical Kinetics I : Rate Laws (Exercises)
- 29: Chemical Kinetics II: Reaction Mechanisms
- 29.1: A Mechanism is a Sequence of Elementary Reactions
- 29.2: The Principle of Detailed Balance
- 29.3: Multiple Mechanisms are Often Indistinguishable
- 29.4: The Steady-State Approximation
- 29.5: Rate Laws Do Not Imply Unique Mechanism
- 29.6: The Lindemann Mechanism
- 29.7: Some Reaction Mechanisms Involve Chain Reactions
- 29.8: A Catalyst Affects the Mechanism and Activation Energy
- 29.9: The Michaelis-Menten Mechanism for Enzyme Catalysis
- 29.E: Chemical Kinetics II: Reaction Mechanisms (Exercises)
- 30: Gas-Phase Reaction Dynamics
- 30.1: The Rate of Bimolecular Gas-Phase Reaction Can Be Calculated Using Hard-Sphere Collision Theory and an Energy-Dependent Reaction Cross Section
- 30.2: A Reaction Cross Section Depends Upon the Impact Parameter
- 30.3: The Rate Constant for a Gas-Phase Chemical Reaction May Depend on the Orientations of the Colliding Molecules
- 30.4: The Internal Energy of the Reactants Can Affect the Cross Section of a Reaction
- 30.5: A Reactive Collision Can Be Described in a Center-of-Mass Coordinate System
- 30.6: Reactive Collisions Can be Studied Using Crossed Molecular Beam Machines
- 30.7: Reactions Can Produce Vibrationally Excited Molecules
- 30.8: The Velocity and Angular Distribution of the Products of a Reactive Collision Provide a Molecular Picture of the Chemical Reaction
- 30.9: Not All Gas-Phase Chemical Reactions Are Rebound Reactions
- 30.10: The Potential-Energy Surface Can Be Calculated Using Quantum Mechanics
- 30.E: Gas-Phase Reaction Dynamics (Exercises)
- 31: Solids and Surface Chemistry
- 31.1: The Unit Cell Is the Fundamental Building Block of a Crystal
- 31.2: The Orientation of a Lattice Plane Is Described by its Miller Indices
- 31.3: The Spacing Between Lattice Planes Can Be Determined from X-Ray Diffraction Measurements
- 31.4: The Total Scattering Intensity Is Related to the Periodic Structure of the Electron Density in the Crystal
- 31.5: The Structure Factor and the Electron Density Are Related by a Fourier Transform
- 31.6: A Gas Molecule can Physisorb or Chemisorb to a Solid Surface
- 31.7: Isotherms are Plots of Surface Coverage as a Function of Gas Pressure at Constant Temperature
- 31.8: The Langmuir Isotherm Can Be Used to Derive Rate Laws for Surface-Catalyzed Gas-Phase Reactions
- 31.9: The Structure of a Surface is Different from that of a Bulk Solid
- 31.10: The Reaction Between H2(g) and N 2(g) to Make NH3 (g) Can Be Surface Catalyzed
- 31.E: Homework Problems
- Math Chapters
1: The Dawn of the Quantum Theory
2: The Classical Wave Equation
3: The Schrödinger Equation and a Particle in a Box
4: Postulates and Principles of Quantum Mechanics
5: The Harmonic Oscillator and the Rigid Rotor
6: The Hydrogen Atom
7: Approximation Methods
8: Multielectron Atoms
9: Chemical Bonding in Diatomic Molecules
10: Bonding in Polyatomic Molecules
11: Computational Quantum Chemistry
12: Group Theory - The Exploitation of Symmetry
13: Molecular Spectroscopy
14: Nuclear Magnetic Resonance Spectroscopy
15: Lasers, Laser Spectroscopy, and Photochemistry
16: The Properties of Gases
17: Boltzmann Factor and Partition Functions
18: Partition Functions and Ideal Gases
19: The First Law of Thermodynamics
20: Entropy and The Second Law of Thermodynamics
21: Entropy & the Third Law of Thermodynamics
22: Helmholtz and Gibbs Energies
23: Phase Equilibria
24: Solutions I: Liquid-Liquid Solutions
25. Solutions II - Solid-Liquid Solutions
26: Chemical Equilibrium
27: The Kinetic Theory of Gases
28: Chemical Kinetics I - Rate Laws
29: Chemical Kinetics II: Reaction Mechanisms
30: Gas-Phase Reaction Dynamics
31: Solids and Surface Chemistry
Math Chapters