1. H y = E y Density-Functional Theory SchrÖdinger Equation Wavefunction
Hamiltonian
H = - (h2/2me)ii2 + i V(ri) + i j e2/rij
Energy
Text Book:
Density-Functional Theory for Atoms and Molecules
by Robert Parr & Weitao Yang

2. Hohenberg-Kohn Theorems
1st Hohenberg-Kohn Theorem: The external potential V(r)
is determined, within a trivial additive constant, by the
electron density r(r).
Implication: electron density determines every thing.

3. 2nd Hohenberg-Kohn Theorem: For a trial density r’(r),
such that r’(r) 0 and  r’(r) dr = N,
E0  Ev[r’(r)]
Implication: Variation approach to determine ground state energy and density.

4. Kohn-Sham Equation
ei yi

7. 1. C.L. Yaws, Chemical Properties Handbook,
Database:
1. C.L. Yaws, Chemical Properties Handbook,
(McGraw-Hill, New York, 1999)
2. D.R. Lide, CRC Handbook of Chemistry and Physics,
3rd ed. (CRC Press, Boca Raton, FL, 2000)
3. J.B . Pedley, R.D. Naylor, S.P. Kirby,
Thermochemical data of organic compounds,
2nd ed. (Chapman and Hall, New York, 1986)
Differences of heat of formation in three references
for same compound are less than 1 kcal/mol; and
error bars are all less than 1kcal/mol
Selected Data: 180 small- or medium-size organic molecules
HKU, 06/11/2013

8. MAD=22.6 kcal/mol

9. B3LYP/6-311+G(d,p) B3LYP/6-311+G(3df,2p)
Hu, Wang, Wong & Chen, J. Chem. Phys. (Comm) (2003)
B3LYP/6-311+G(d,p)
B3LYP/6-311+G(3df,2p)
MAD=22.6 kcal/mol
MAD=11.6 kcal/mol
MAD=1.59 kcal/mol
MAD=1.45 kcal/mol