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Quantum Chapter 8 2016
Quantum Chapter 8 2016
é h2 2 Z I e2 e2 Z I Z J e2 ù
H = ê- å Ñi - å +å +å ú
êë i 2m e iI 4pe |
0 ir - RI | j <i 4pe r
0 ij I >J 4pe0 | RI - RJ | úû
Hartree-Fock equations
1
Y ( r1 , r2 ,.., rN ) = det | j 1 ( r1 )j 2 ( r2 )..j N ( rN ) |
N!
Where the φ(r) is an atomic type orbital. We need to write there
using some basis functions ξ(r)(simple known functions that
contain adjustable parameters. Typically the basis functions are
centered to atoms, ξ(r-R).
( ) = , ( )
=
Where C contain all the molecular coefficients, F is the Fock
matrix and S is the overlap matrix. The Fock matrix is
= + −
ħ
=∫ ( ) − ∇ − ∑ ( )
| |
= ( | ) = ( | )
( ) ( ) ( ) ( )
( | )= = , ,
| − |
= ( ) ( )
Is DC(n)small
Solve F(n)C’(n+1)=S C’(n+1)
enough
The next issue is the basis functions, ξ(r). There are several
possibilities but the most common functions are gaussians
( )= ( )exp (− ) ( , )
The Pn(r) is some polynomial to make the functions more atomic
like and Ylm are the spherical harmonic functions. It would be
nice to use atomic type functions (Slater functions) but the J
and K integrals become tedious with them. With gaussians these
integrals can be done analytically but we need more Gaussians to
get good accuracy. It is close to an art to make a good Gaussian
basis. Typically we need higher angular momentums than the
valence electrons have, e.q. d-orbital for C, O, N etc. We need
two (or even more) exponents since in the molecule the wave
functions decay from the nucleus is not symmetric.
The geometries are good but most bonds are a bit too short.
We need to discuss a bit how to optimize the molecules geometry
using the HF theory. We can compute the total electronic energy
of the system. That depend of the atomic positions. Then we can
compute the forces acting on each atom
( ,.. ); =−
There are many ways to improve the HF method. Most of them are
very technical and in this course only the basic ideas behind
them are given. But we can first “define” the correlation
energy. There is the best non-relativistic total energy with
Born-Oppenheimer approximation of the system Etot, the
correlation energy is the difference
Ψ( , . . )= Ψ + Ψ + Ψ + . ..
, ,
The new determinants are built form the HF orbitals but the
electrons are also placed on exited states. The notation Ψ
means that one electron is excited from state i to state a,
similarly Ψ means that two electrons are excited from states i
and j to states a and b. This wave functions is denoted as CISD
(CI with singlet and double excitations). The Ψ is the Slater
determinant (or the HF wave functions). All the excited
determinants are orthogonal to the HF wf (and each other). In
the CI calculations the HF orbitals are kept constant and the a
coefficients are optimized.
Scaling Method
N4 HF
N5 MP2
N7 MP4, CCSD(T)
Perturbation methods
( )
= +
We can next write the energy and wave functions as a power
series of l.
( ) ( ) ( ) ( ) ( ) ( )
= + + +⋯ = + + +⋯
Now we can write hierarchical equation for each power of l
( ) ( ) ( ) ( )
=
( ) ( ) ( ) ( ) ( ) ( ) ( )
+ = +
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
+ = + +
( ) ( )
The different level wave functions are orthogonal = .
( )
So we can solve , Ψ( ), ( )
etc.
( ) ( )〉
( ) 〈 ( )
( )
=〈 ( ) ( )〉 ( )
=〈 ( ) ( )〉
=∑ ( ) ( )
( ) ( )〉
( )
〈
= ( ) ( )
−
1 1
= − ( − )
− 2
( )
[( | ) − ( | )]
=
+ − −
,
The i,j denote occupied state and a,b unoccupied states. This
the first real correction and it is called the MP2 theory. (The
E(0) + E(1) is in fact the HF energy). The perturbation theory can
be to arbitrary level. The different levels are denotes as MPn.
Of these the most important is the MP2. It is rather fast and
causes a significant correction to HF. The MP3 is a
disappointment since it does not corrects much the MP2. The MP4
is somewhat better but it is already very expensive. The higher
terms are not used and in some model systems it has been shown
that the MPn series do not converge.
Last the basis set needed for well converged CI and MPn methods
is larger than in the HF calculations. This is bad news since
these post-HF methods have poorer scaling behavior than HF so
the computations become quickly very time consuming.
Y ( r1 , r2 ,.., rN ) a Y [n ( r ) ]
This wave function is much much simpler than the true wf. The
problem is that we do not know the equations to solve the wf.
The basic ideas are form Kohn, Hohenberg and Sham (1963, 1964,
Kohn Nobel prize 1998). Even we do not know the correct equation
it is useful to try to find a good approximation for it. Kohn
and Sham showed that a single Slater determinant type wf with
simple model for the Exchange and Correlation (XC) energy will
give good results. The formulation is quite similar as for the
HF.
= + −
ħ
=∫ ( ) − ∇ − ∑ ( )
| |
= ( ( ), ∇ ( ) , . . ) ; =
( )
( ) ( )
= ( ) = , ( )
| − |
,
One can also mix the HF and DFT theories. These are called
hybrid methods and they also are rather accurate. The most
common of them is the B3LYP model also PBE0 model is good.
They show that B3LYP method is usually as good as MP2. Even the
tables shows only one DFT method the general trend is correct.
In most cases the DFT methods are as good as or better than MP2.
There are more tables in Engels book. Almost all methods the
bond distances are quite good. For energies the HF or LDA are
not reliable whereas most GGA’s and correlated quantum chemistry
methods are good. The reaction barriers are challenging form
computational methods and in them the GGA methods work rather
well.
Naturally the GGA methods have some problems. One of them is the
van der Waals interactions (or dispersion) which is important in
weakly bonded systems. Basically HF and GGA will do not have
them and they have to be added using additional (empirical)
terms. In most cases such PBE-D3 models works well. DFT have
also problems to describe the hydrogen correctly. Like HF the
DFT models do not give good HOMO-LUMO gap.