Electron Density

Functional Theory
Lecture notes (rough draft)

October 2010

Roi Baer

Institute of Chemistry,
The Fritz Haber Center for Molecular Dynamics
The Hebrew University of Jerusalem,
Jerusalem, 91904 Israel

Roi Baer

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Contents

I. INTRODUCTORY BACKGROUND TOPICS ............... ERROR! BOOKMARK NOT

DEFINED.

A. THE SCHRDINGER EQUATION ................................. ERROR! BOOKMARK NOT DEFINED.

B. BOSONS AND FERMIONS ............................................. ERROR! BOOKMARK NOT DEFINED.
I. GROUND-STATE WAVE FUNCTION OF BOSONS ........... ERROR! BOOKMARK NOT DEFINED.
II. GROUND-STATE WAVE FUNCTION OF FERMIONS ...... ERROR! BOOKMARK NOT DEFINED.
C. WHY ELECTRONIC STRUCTURE IS AN IMPORTANT DIFFICULT PROBLEM .......... ERROR!
BOOKMARK NOT DEFINED.
D. THE BORN-OPPENHEIMER THEORY ......................... ERROR! BOOKMARK NOT DEFINED.
I. THE ADIABATIC THEOREM .......................................... ERROR! BOOKMARK NOT DEFINED.
II. MOTIVATION FOR THE BORN-OPPENHEIMER APPROXIMATION: CLASSICAL NUCLEI
ERROR! BOOKMARK NOT DEFINED.
III. THE BORN-OPPENHEIMER APPROXIMATION IN QUANTUM NUCLEAR CASE ........... ERROR!
BOOKMARK NOT DEFINED.
E. ELECTRON CORRELATION ......................................... ERROR! BOOKMARK NOT DEFINED.
I. THE ELECTRONIC WAVE FUNCTION OF TWO NON-INTERACTING ELECTRONS .......... ERROR!
BOOKMARK NOT DEFINED.
II. CORRELATION IN ACTION: A WAVE FUNCTION OF 2 INTERACTING PARTICLES IN AN
HARMONIC TRAP .............................................................. ERROR! BOOKMARK NOT DEFINED.
F. THE ELECTRON DENSITY IS A MUCH SIMPLER OBJECT THAN THE WAVE FUNCTION
ERROR! BOOKMARK NOT DEFINED.
G. THE VARIATIONAL PRINCIPLE .................................. ERROR! BOOKMARK NOT DEFINED.
H. DILATION RELATIONS ................................................ ERROR! BOOKMARK NOT DEFINED.
I. THE CONCEPT OF THE VIRIAL IN CLASSICAL MECHANICS............ERROR! BOOKMARK NOT
DEFINED.

II. THE VIRIAL THEOREM IN QUANTUM MECHANICS ..... ERROR! BOOKMARK NOT DEFINED.
III. SLATERS THEORY OF THE CHEMICAL BOND USING THE VIRAL THEOREM ............ ERROR!
BOOKMARK NOT DEFINED.
IV. OTHER DILATION FACTS .......................................... ERROR! BOOKMARK NOT DEFINED.
I. INTRODUCTION TO FUNCTIONALS ............................. ERROR! BOOKMARK NOT DEFINED.
I. DEFINITION OF A FUNCTIONAL AND SOME EXAMPLES ERROR! BOOKMARK NOT DEFINED.

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II. LINEAR FUNCTIONALS ............................................... ERROR! BOOKMARK NOT DEFINED.
III. FUNCTIONAL DERIVATIVES...................................... ERROR! BOOKMARK NOT DEFINED.
IV. INVERTIBLE FUNCTION FUNCTIONALS AND THEIR FUNCTIONAL DERIVATIVES ..... ERROR!
BOOKMARK NOT DEFINED.
V. CONVEX FUNCTIONALS ............................................ ERROR! BOOKMARK NOT DEFINED.
J. MINIMIZING FUNCTIONALS IS AN IMPORTANT PART OF DEVELOPING A DFT .... ERROR!
BOOKMARK NOT DEFINED.
I. MINIMIZATION OF FUNCTIONS.................................... ERROR! BOOKMARK NOT DEFINED.
II. CONSTRAINED MINIMIZATION: LAGRANGE MULTIPLIERS..........ERROR! BOOKMARK NOT
DEFINED.

III. MINIMIZATION OF FUNCTIONALS ............................. ERROR! BOOKMARK NOT DEFINED.

II. MY FIRST DENSITY FUNCTIONAL: THOMAS-FERMI THEORY ........ ERROR!

BOOKMARK NOT DEFINED.

A. BASIC CONCEPTS IN THE ELECTRON GAS AND THE THOMAS-FERMI THEORY .. ERROR!
BOOKMARK NOT DEFINED.
B. MINIMIZATION OF THE THOMAS-FERMI ENERGY ... ERROR! BOOKMARK NOT DEFINED.
C. THOMAS-FERMI DOES NOT ACCOUNT FOR MOLECULES ......... ERROR! BOOKMARK NOT
DEFINED.

D. THOMAS-FERMI SCREENING ..................................... ERROR! BOOKMARK NOT DEFINED.

E. VON WEIZSCKER KINETIC ENERGY ........................ ERROR! BOOKMARK NOT DEFINED.

III. MANY-ELECTRON WAVE FUNCTIONS ................. ERROR! BOOKMARK NOT

DEFINED.

A. THE ELECTRON SPIN .................................................. ERROR! BOOKMARK NOT DEFINED.

B. THE PAULI PRINCIPLE ................................................ ERROR! BOOKMARK NOT DEFINED.
C. THE EXCITED STATES OF THE HELIUM ATOM ......... ERROR! BOOKMARK NOT DEFINED.
D. THE SLATER WAVE FUNCTION IS THE BASIC ANTI-SYMMETRIC FUNCTION
DESCRIBING N ELECTRONS IN N ORBITALS ...................... ERROR! BOOKMARK NOT DEFINED.

E. WITHOUT LOSS OF GENERALITY, WE MAY ASSUME THE ORBITALS OF A SLATER

WAVE FUNCTION ARE ORTHOGONAL ................................ ERROR! BOOKMARK NOT DEFINED.

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F. ANY ANTISYMMETRIC FUNCTION CAN BE EXPANDED AS A SUM OF BASIC SLATER
(DETERMINANTAL) FUNCTIONS ......................................... ERROR! BOOKMARK NOT DEFINED.
G. DETERMINANT EXPECTATION VALUES ..................... ERROR! BOOKMARK NOT DEFINED.
I. ONE-BODY OPERATORS .............................................. ERROR! BOOKMARK NOT DEFINED.
II. TWO-BODY OPERATORS ............................................ ERROR! BOOKMARK NOT DEFINED.

IV. THE HARTREE-FOCK THEORY ............ ERROR! BOOKMARK NOT DEFINED.

A. THE HARTREE-FOCK ENERGY AND EQUATIONS ..... ERROR! BOOKMARK NOT DEFINED.
B. RESTRICTED CLOSED-SHELL HARTREE-FOCK ........ ERROR! BOOKMARK NOT DEFINED.
C. ATOMIC ORBITALS AND GAUSSIAN BASIS SETS ....... ERROR! BOOKMARK NOT DEFINED.
D. VARIATIONAL-ALGEBRAIC APPROACH HARTREE-FOCK ....... ERROR! BOOKMARK NOT
DEFINED.

E. THE ALGEBRAIC DENSITY MATRIX AND CHARGE ANALYSIS. ERROR! BOOKMARK NOT
DEFINED.

F. SOLVING THE HARTREE-FOCK EQUATIONS ............. ERROR! BOOKMARK NOT DEFINED.

I. DIRECT INVERSION IN ITERATIVE SPACE (DIIS) ......... ERROR! BOOKMARK NOT DEFINED.
II. DIRECT MINIMIZATION ............................................. ERROR! BOOKMARK NOT DEFINED.
G. PERFORMANCE OF THE HARTREE-FOCK APPROXIMATION ... ERROR! BOOKMARK NOT
DEFINED.

H. BEYOND HARTREE-FOCK .......................................... ERROR! BOOKMARK NOT DEFINED.

V. ADVANCED TOPICS IN HARTREE-FOCK THEORY .......ERROR! BOOKMARK

NOT DEFINED.

A. LOW-LYING EXCITATIONS AND THE STABILITY OF THE HARTREE-FOCK GROUND

STATE .................................................................................. ERROR! BOOKMARK NOT DEFINED.

I. CI-SINGLES AND BRILLOUINS THEOREM .................. ERROR! BOOKMARK NOT DEFINED.

II. HARTREE-FOCK STABILITY ....................................... ERROR! BOOKMARK NOT DEFINED.
B. KOOPMANS THEOREM .............................................. ERROR! BOOKMARK NOT DEFINED.
C. FRACTIONAL OCCUPATION NUMBERS, THE HF ORBITAL FUNCTIONAL AND THE
GENERALIZED KOOPMANS THEOREM ............................. ERROR! BOOKMARK NOT DEFINED.

D. HARTREE-FOCK FOR THE HOMOGENEOUS ELECTRON GAS .... ERROR! BOOKMARK NOT
DEFINED.

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I. HARTREE-FOCK ORBITALS AND ORBITAL ENERGIES OF HEG .....ERROR! BOOKMARK NOT
DEFINED.

II. THE DENSITY OF STATES OF THE HEG ...................... ERROR! BOOKMARK NOT DEFINED.
III. STABILITY OF THE HEG IN HARTREE-FOCK THEORY ...............ERROR! BOOKMARK NOT
DEFINED.

VI. THE HOHENBERG-KOHN DENSITY THEORY ..... ERROR! BOOKMARK NOT

DEFINED.

A. THE FIRST HK THEOREM .......................................... ERROR! BOOKMARK NOT DEFINED.

B. THE HK FUNCTIONAL ................................................ ERROR! BOOKMARK NOT DEFINED.
C. MINIMUM PRINCIPLE FOR DENSITY FUNCTIONAL THEORY .... ERROR! BOOKMARK NOT
DEFINED.

D. AN INTERESTING OBSERVATION ON THE VARIATIONAL PRINCIPLE OF NON-

INTERACTING ELECTRONS ................................................. ERROR! BOOKMARK NOT DEFINED.

E. THE SET OF V-REPRESENTABILE DENSITIES ............. ERROR! BOOKMARK NOT DEFINED.

I. V-REP DENSITIES CORRESPOND TO GROUND STATES WAVE FUNCTION OF SOME POTENTIAL
WELL ................................................................................. ERROR! BOOKMARK NOT DEFINED.

II. SOME NON-V-REPRESENTABILIT ISSUES .................... ERROR! BOOKMARK NOT DEFINED.

III. THE SET OF V-REP DENSITIES OF A GIVEN ELECTRON NUMBER IS NOT CONVEX .... ERROR!
BOOKMARK NOT DEFINED.
F. LEVY-LIEB GENERALIZATION OF THE HK FUNCTIONAL ........ ERROR! BOOKMARK NOT
DEFINED.

G. THE DILATION INEQUALITY FOR THE HK FUNCTIONAL ......... ERROR! BOOKMARK NOT
DEFINED.

VII. THE KOHN-SHAM METHOD ................. ERROR! BOOKMARK NOT DEFINED.

A. NON-INTERACTING ELECTRONS ................................ ERROR! BOOKMARK NOT DEFINED.

B. ORBITALS FOR THE NON-INTERACTING ELECTRONSERROR! BOOKMARK NOT DEFINED.
C. THE CORRELATION ENERGY FUNCTIONAL: DEFINITION AND SOME FORMAL
PROPERTIES ........................................................................ ERROR! BOOKMARK NOT DEFINED.

D. THE KOHN SHAM EQUATIONS ................................... ERROR! BOOKMARK NOT DEFINED.

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I. THE KOHN-SHAM EQUATION FROM A SYSTEM OF NON-INTERACTING PROBLEM .... ERROR!
BOOKMARK NOT DEFINED.
II. SYSTEMS WITH PARTIALLY OCCUPIED ORBITALS...... ERROR! BOOKMARK NOT DEFINED.
III. IS THE GROUND STATE WAVE FUNCTION OF NON-INTERACTING PARTICLES ALWAYS A
SLATER WAVE FUNCTION ................................................. ERROR! BOOKMARK NOT DEFINED.
IV. JANAKS THEOREM .................................................. ERROR! BOOKMARK NOT DEFINED.
E. VIRIAL THEOREM RELATED IDENTITIES IN DFT . ERROR! BOOKMARK NOT DEFINED.
F. GALILEAN INVARIANCE.............................................. ERROR! BOOKMARK NOT DEFINED.
G. HOLES AND THE ADIABATIC CONNECTION ............... ERROR! BOOKMARK NOT DEFINED.
I. THE EXCHANGE AND CORRELATION HOLES ............... ERROR! BOOKMARK NOT DEFINED.
II. THE FERMI-COULOMB HOLE FOR HARMONIC ELECTRONS .........ERROR! BOOKMARK NOT
DEFINED.

III. THE FERMI HOLE IN THE NON-INTERACTING SYSTEM ...............ERROR! BOOKMARK NOT
DEFINED.

IV. THE ADIABATIC CONNECTION ................................. ERROR! BOOKMARK NOT DEFINED.

H. DERIVATIVE DISCONTINUITY IN THE EXCHANGE CORRELATION POTENTIAL
FUNCTIONAL ....................................................................... ERROR! BOOKMARK NOT DEFINED.

VIII. APPROXIMATE CORRELATION ENERGY FUNCTIONALS ............. ERROR!

BOOKMARK NOT DEFINED.

A. THE LOCAL DENSITY APPROXIMATION (LDA) ......... ERROR! BOOKMARK NOT DEFINED.
I. THE EXCHANGE ENERGY PER ELECTRON IN THE HEG ERROR! BOOKMARK NOT DEFINED.
II. CORRELATION ENERGY OF THE HEG: THE HIGH DENSITY LIMIT ...... ERROR! BOOKMARK
NOT DEFINED.

III. CORRELATION ENERGY OF THE HEG: THE LOW DENSITY LIMIT AND THE WIGNER
CRYSTAL ........................................................................... ERROR! BOOKMARK NOT DEFINED.

IV. MONTE-CARLO DETERMINATION OF THE CORRELATION ENERGY FOR THE HEG . ERROR!
BOOKMARK NOT DEFINED.
V. THE POLARIZED HEG; LOCAL SPIN-DENSITY APPROXIMATION (LSDA) ................ ERROR!
BOOKMARK NOT DEFINED.
VI. SUCCESSES AND FAILURES OF LSDA ....................... ERROR! BOOKMARK NOT DEFINED.
VII. PLAUSIBLE REASONS FOR THE SUCCESS OF LSDA . ERROR! BOOKMARK NOT DEFINED.

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B. SEMILOCAL FUNCTIONALS AND THE GENERALIZED GRADIENT APPROXIMATION
ERROR! BOOKMARK NOT DEFINED.

IX. GENERALIZED KOHN-SHAM APPROACHES ....... ERROR! BOOKMARK NOT

DEFINED.

A. THE GENERALIZED KOHN-SHAM FRAMEWORK ...... ERROR! BOOKMARK NOT DEFINED.

B. KOHN-SHAM FROM GENERALIZED KS ..................... ERROR! BOOKMARK NOT DEFINED.
C. THE HYBRID FUNCTIONAL OF BECKE ...................... ERROR! BOOKMARK NOT DEFINED.
D. ......................................................................................... ERROR! BOOKMARK NOT DEFINED.
E. LONG-RANGE SELF-REPULSION AND LACK OF DERIVATIVE DISCONTINUITY .... ERROR!
BOOKMARK NOT DEFINED.
F. RANGE SEPARATED HYBRIDS ..................................... ERROR! BOOKMARK NOT DEFINED.
G. ORBITAL FUNCTIONALS AND OPTIMIZED EFFECTIVE POTENTIALSERROR! BOOKMARK
NOT DEFINED.

H. APPROXIMATE CORRELATION FUNCTIONALS AND THE BORN-OPPENHEIMER FORCE

ON NUCLEI........................................................................... ERROR! BOOKMARK NOT DEFINED.

X. MORE ON THE DFT CORRELATION ENERGY ...... ERROR! BOOKMARK NOT

DEFINED.

A. APPROXIMATIONS TO EX ARE APPROXIMATION TO EC ........... ERROR! BOOKMARK NOT

DEFINED.

B. THE NECESSITY OF LONG-RANGE PARAMETER TUNING .......... ERROR! BOOKMARK NOT

DEFINED.

I. THE SYMMETRIC RADICAL CATION ............................ ERROR! BOOKMARK NOT DEFINED.

II. AROMATIC DONOR -TCNE ACCEPTOR CHARGE TRANSFER EXCITATION ................ ERROR!
BOOKMARK NOT DEFINED.

XI. TDDFT ........................................................... ERROR! BOOKMARK NOT DEFINED.

A. TIME-DEPENDENT LINEAR RESPONSE THEORY ....... ERROR! BOOKMARK NOT DEFINED.

B. ALGEBRAIC APPROACH TO LINEAR RESPONSE ........ ERROR! BOOKMARK NOT DEFINED.
C. FREQUENCY-DOMAIN RESPONSE ............................... ERROR! BOOKMARK NOT DEFINED.

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D. EXCITATION ENERGIES FROM THE ALGEBRAIC TREATMENT . ERROR! BOOKMARK NOT
DEFINED.

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