Contents of Mike Colvin' Introduction to Quantum Chemistry(New)

Introduction to Quantum Chemistry

[Revised Edition]

Mike Colvin

Contents

How Are Quantum Chemical Methods Used?

Overview: What will the methods be used for?

Quantum Mechanics

MolecularParticles

The Molecular Schrodinger Equation:

Born-Oppenheimer Approximation

Electronic Schrodinger Equation

Electron Spin

Slater Determinants

Determinants

Restricted and Unrestricted

Hartree-Fock:

1.The HF method

The Fock Operator

Introduction of a Basis Set: The Roothan Matrix Equations

Direct Hartree-Fock Algorithm

Hartree-Fock Gradients and 2nd Derivatives

Restricted and Unrestricted Hartree-Fock

Multi-Determinants Spin Eigenfunctions

UHF Instabilities

2.Basis Sets

Gaussian Type Orbitals

Angular Dependence of Basis Functions

Polarization and Diffuse Basis Functions

Taxonomy of Basis Sets: Huzinaga-Dunning

Taxonomy of Basis Sets 2: Pople Basis Sets

Basis Set Superposition Error

Where to Get Basis Sets

Basis Set Input in Gaussian 9X Format

Role of HF in Quantum Chemical Protocol

3.Accuracy of Hartree Fock Chemical Properties

HF Predicted Bond Lengths

HF Structural Properties: Open Shells

Structural Properties for Large Molecules

                     HF Predicted Rotational Barriers
                     Hartree-Fock Isomerization Reaction Energies
                     Hartree-Fock Entropies
                     Caveat Emptor
                     UHF & RHF Poor at Homolytic Bond Breaking:

Isodesmic and Isogyric Reactions

4.Charges and other properties

Atomic Charges

Mulliken Populations

Natural Atomic Orbital Populations

                     Basis Set Dependence of Atomic Charge Methods
                     Chemical Meaning of Atomic Charges

                     Molecular Orbitals
                     Ionization Potentials, Electron Affinities and Koopman's Theorem
                     Frontier Molecular Orbital Theory
                     NMR Chemical Shifts

Electron Correlation Methods:

1.Part 1:

Conceptual View of Correlation Effects

Basis Sets and Levels of Theory

Methylene Singlet-Triplet Splitting:

Predicted Methylene Singlet-Triplet Splittings

Splitting using mixed-basis set methods

Perturbation Theory:

Moller - Plesset Perturbation Theory

Convergence of Møller-Plesset Expansion

Variational Principle

Configuration Interaction

2.Part 2:

Size Consistency

Coupled Cluster Methods

Multiconfiguration SCF

Density Functional Theory (DFT):

Examples Of DFT Functionals

Computational Costs of HF and Correlated Methods

Accuracy of Correlated Methods

Accuracy of Correlated Methods (2)

Accuracy of Correlated Methods (3)

Accuracy of Correlated Methods (4)

Empirically-Corrected QC Protocols

"Gaussian" Theory

Summary: Quantum Chemical Wavefunctions (and their acronyms)

Semiempirical Methods:

Semi-Empirical Quantum Chemistry

Huckel MO Theory:

The Huckel Secular Equations

Benzene Huckel Solutions:

Limitations of Huckel Method

Neglect of Diffential Overlap:

MNDO and MINDO Parameter Sets (1985)

Accuracy of Semi-empirical Methods

Examples of Quantum Chemical Studies :

PAH Combustion:

AIA Mutagens:

Properties Included in Quantum Chemical QSAR:

Significant Predictors of Log MP

Relationship of Nitrenium Stability to LUMO Energy

Hydride Shift Energies:

Quantum Chemistry Software:

Standard Quantum Chemistry Software (commercial):

Gaussian 94

ACES II

Spartan

Mulliken

Quantum Chemistry Software (2)

Standard Quantum Chemistry Software (free)

Gamess

Columbus

Argus

MOPAC

Anatomy of a QC Input

Specification of Molecular Geometries: Cartesian and Z-Matrix

Example of a Gaussian 94 Input File

The more accurate the calculations become, the more the concepts tend to vanish into thin air.

[R. S. Mulliken, J. Chem. Phys. 43, S2 (1965)]