量子化学（第3版）

preface to the third edition

preface to the second edition

preface to the first edition

1classical waves and the time-independent schrodinger waveequation

1-1introduction

1-2waves

1-3the classical wave equation

1-4standing waves in a clamped string

1-5light as an electromagnetic wave

1-6the photoelectric effect

1-7the wave nature of matter

1-8a diffraction experiment with electrons

1-9schrodinger's time-independent wave equation

1-10conditions on

1-11some insight into the schrodinger equation

1-12summary

problems

multiple choice questions

reference

2quantum mechanics of some simple systems

2-1the particle in a one-dimensional \box\.

2-2detailed examination of particle-in-a-box solutions

2-3the particle in a one-dimensional \box\ with one finitewall

2-4the particle in an infinite \box\ with a finite centralbarrier

2-5the free particle in one dimension

2-6the particle in a ring of constant potential

2-7the particle in a three-dimensional box: separation ofvariables

2-8the scattering of particles in one dimension

2-9summary

problems

multiple choice questions

references

3the one-dimensional harmonic oscillator

3-1introduction

2-2some characteristics of the classical one-dimensionalharmonic oscillator

3-3the quantum-mechanical harmonic oscillator

3-4solution of the harmonic oscillator schrtdingerequation

3-5quantum-mechanical average value of the potentialenergy

3-6vibrations of diatomic molecules

3-7summary

problems

multiple choice questions

the hydrogenlike ion, angular momentum, and the rigidrotor

4-1the schrodinger equation and the nature of its solutions

4-2separation of variables

4-3solution of the and equations

4-4 atomic units

4-5angular momentum and spherical harmonics

4-6 angular momentum and magnetic moment

4-7angular momentum in molecular rotation--the rigidrotor

4-8summary

problems

multiple choice questions

references

5many-electron atoms

5-1the independent electron approximation

5-2simple products and electron exchange symmetry

5-3electron spin and the exclusion principle

5-4slater determinants and the pauli principle

5-5singlet and triplet states for the ls2s configuration ofhelium

5-6the self-consistent field, slater-type orbitals, and theaufbau

principle

5-7electron angular momentum in atoms

5-8overview

problems

multiple choice questions

references

6postulates and theorems of quantum mechanics

6-1 introduction

6-2 the wavefunction postulate

6-3 the postulate for constructing operators

6-4 the time-dependent schrrdinger equation postulate

6-5 the postulate relating measured values toeigenvalues

6-6 the postulate for average values

6-7 hermitian operators

6-8 proof that eigenvalues of hermitian operators arereal

6-9 proof that nondegenerate eigenfunctions of a hermitianoperator

form an orthogonal set

6-10demonstration that all eigenfunctions of a hermitianoperator may be expressed as an orthonormal set

6-11proof that commuting operators have simultaneouseigenfunctions

6-12completeness of eigenfunctions of a hermitianoperator

6-13the variation principle

6-14the pauli exclusion principle

6-15measurement, commutators, and uncertainty

6-16time-dependent states

6-17summary

problems

multiple choice questions

references

7the variation method

7-1 the spirit of the method

7-2 nonlinear variation: the hydrogen atom

7-3 nonlinear variation: the helium atom

7-4 linear variation: the polarizability of the hydrogenatom

7-5 linear combination of atomic orbitals: the hemolecule-ion

7-6 molecular orbitals of homonuclear diatomicmolecules

7-7 basis set choice and the variational wavefunction

7-8 beyond the orbital approximation

problems

multiple choice questions

references

8the simple hiickel method and applications

8-1 the importance of symmetry

8-2 the assumption of ar-π separability

8-3 the independent π-electron assumption

8-4 setting up the htickel determinant

8-5 solving the hmo determinantal equation for orbitalenergies

8-6 solving for the molecular orbitals

8-7 the cyclopropenyl system: handling degeneracies

8-8 charge distributions from hmos

8-9 some simplifying generalizations

8-10 hmo calculations on some simple molecules

8-11summary: the simple hmo method for hydrocarbons

8-12relation between bond order and bond length

8-13π-electron densities and electron spin resonancehyperfine splitting constants

8-14orbital energies and oxidation-reductionpotentials

8-15orbital energies and ionization energies

8-16π-electron energy and aromaticity

8-17extension to heteroatomic molecules

8-18self-consistent variations of at and/5

8-19hmo reaction indices

8-20conclusions

problems

multiple choice questions

references

matrix formulation of the linear variation method

9-1introduction

9-2matrices and vectors

9-3matrix formulation of the linear variation method

9-4solving the matrix equation

9-5summary

problems

references

10 the extended hiickel method

10-1the extended htickel method

10-2mulliken populations

10-3extended htickel energies and mulliken populations

10-4extended htickel energies and experimentalenergies

problems

references

11 the scf-lcao-mo method and extensions

11-1ab lnitio calculations

11-2the molecular hamiltonian

11-3the form of the wavefunction

11-4the nature of the basis set

11-5the lcao-mo-scf equation

11-6interpretation of the lcao-mo-scf eigenvalues

11-7the scf total electronic energy

11-8basis sets

11-9the hartree-fock limit

11-10correlation energy

11-11koopmans' theorem

11-12configuration interaction

11-13size consistency and the m011er-plesset and coupledcluster

treatments of correlation

11-14multideterminant methods

11-15density functional theory methods

11-16examples of ab initio calculations

11-17approximate scf-mo methods

problems

references

12 time-independent rayleigh-schr6dinger perturbation theory

12-1an introductory example

12-2formal development of the theory for nondegeneratestates..

12-3a uniform electrostatic perturbation of an electron in a\wire\

12-4the ground-state energy to first-order of heliumlikesystems

12-5perturbation at an atom in the simple htickel momethod

12-6perturbation theory for a degenerate state

12-7polarizability of the hydrogen atom in the n = 2states

12-8degenerate-level perturbation theory by inspection

12-9interaction between two orbitals: an important chemicalmodel

12-10connection between time-independent perturbation theoryand

spectroscopic selection rules

problems

multiple choice questions

references

13 group theory

13-1introduction

13-2an elementary example

13-3symmetry point groups

13-4the concept of class

13-5symmetry elements and their notation

13-6identifying the point group of a molecule

13-7representations for groups

13-8generating representations from basis functions

13-9labels for representations

13-10some connections between the representation table andmolecul orbitals

13-11representations for cyclic and related groups

13-12orthogonality in irreducible inequivalentrepresentations

13-13characters and character tables

13-14using characters to resolve reduciblerepresentations

13-15identifying molecular orbital symmetries

13-16determining in which molecular orbital an atomicorbital wi appear

13-17generating symmetry orbitals

13-18hybrid orbitals and localized orbitals

13-19symmetry and integration

problems

multiple choice questions

references

14 qualitative molecular orbital theory

14-1the need for a qualitative theory

14-2hierarchy in molecular structure and in molecularorbitals

14-3h+ revisited

14-4h2: comparisons with h+2

14-5rules for qualitative molecular orbital theory

14-6application of qmot rules to homonuclear diatomicmolecules

14-7shapes of polyatomic molecules: walsh diagrams

14-8frontier orbitals

14-9qualitative molecular orbital theory of reactions

problems

references

15 molecular orbital theory of periodic systems

15-1introduction

15-2the free particle in one dimension

15-3the particle in a ring

15-4benzene

15-5general form of one-electron orbitals in periodicpotentials--bloch's theorem

15-6a retrospective pause

15-7an example: polyacetylene with uniform bondlengths

15-8electrical conductivity

15-9polyacetylene with alternating bond lengths--peierls'distortion

15-10electronic structure of all-trans polyacetylene

15-11comparison of ehmo and scf results onpolyacetylene

15-12effects of chemical substitution on the π bands

15-13poly-paraphenylene--a ring polymer

15-14energy calculations

15-15two-dimensional periodicity and vectors in reciprocalspace

15-16periodicity in three dimensions--graphite

15-17summary

problems

references

appendix 1useful integrals

appendix 2determinants

appendix 3evaluation of the coulomb repulsion integral overis aos

appendix 4angular momentum rules

appendix 5the pairing theorem

appendix 6hiickel molecular orbital energies, coefficients,electron densities, and bond orders for some simple molecules

appendix 7derivation of the hartree-fock equation

appendix 8the viriai theorem for atoms and diatomicmolecules

contents

appendix 9bra-ket notation

appendix 10values of some useful constants and conversionfactor,

appendix 11group theoretical charts and tables

appendix 12hints for solving selected problems

appendix 13answers to problems

index