Lecture 4.
Perturbation theory September 22 1 / 17
Introduction to Computational Chemistry
Vesa Hanninen
Laboratory of Physical Chemistry
Chemicum 4th oor
vesa.hanninen@helsinki.
September 20, 2012
Perturbation theory
Lecture 4. Perturbation theory September 22 2 / 17
Introduction:
The MllerPlesset perturbation theory (MP) was published as early as 1934
by Christian Mller and Milton S. Plesset.
I The starting point is eigenfunction of the Fock-operator.
I It improves on the HartreeFock method by adding electron correlation
eects.
I MP theory is not variational. Calculated energy may be lower than true
ground state energy.
MP methods (MP2, MP3, MP4, ...) are implemented in many computational
chemistry codes. Higher level MP calculations, generally only MP5, are
possible in some codes. However, they are rarely used because of their costs.
Quantum mechanical perturbation theory
Lecture 4. Perturbation theory September 22 3 / 17
The Scrodinger equation for the perturbed state
n
is
H
n
= (
H
(0)
+
V )
n
= E
n
n
(1)
where is an arbitrary real parameter,
V is a perturbation to the unperturbed
Hamiltonian
H
(0)
, and subscript n = 1, 2, 3, ... denotes dierent discrete
states.
I The expressions produced by perturbation theory are not exact
I Accurate results can be obtained as long as the expansion parameter
is very small.
We expand
n
and E
n
in Taylor series in powers of . The eigenvalue
equation becomes
(
H
(0)
+
V )(
i=0
(i)
n
) = (
i=0
i
E
(i)
n
)(
i=0
(i)
n
) (2)
Quantum mechanical perturbation theory
Lecture 4. Perturbation theory September 22 4 / 17
Writing only the rst terms we obtain
(
H
(0)
+
V )(
(0)
n
+
(1)
n
) = (E
(0)
n
+E
(1)
n
)(
(0)
n
+
(1)
n
) (3)
The zeroth-order equation is simply the Schrodinger equation for the
unperturbed system
H
(0)
(0)
n
= E
(0)
n
(0)
n
(4)
The rst-order terms are those which are multiplied by
H
(0)
(1)
n
+
V
(0)
n
= E
(0)
n
(1)
n
+E
(1)
n
(0)
n
(5)
When this is multiplied through by
(0)
n
and integrated, the rst term on the
left-hand side cancels with the rst term on the right-hand side (The
H
(0)
is
hermitian). This leads to the rst-order energy shift:
E
(1)
n
=
(0)
n
(0)
n
(6)
This is simply the expectation value of the perturbation Hamiltonian while the
system is in the unperturbed state.
Quantum mechanical perturbation theory
Lecture 4. Perturbation theory September 22 5 / 17
Interpretation of the rst order correction to energy:
E
(1)
n
=
(0)
n
(0)
n
(7)
I The perturbation is applied, but we keep the system in the quantum
state |
(0)
n
, which is a valid quantum state though no longer an energy
eigenstate.
I The perturbation causes the average energy of this state to increase by
(0)
n
|V |
(0)
n
.
I The true energy shift is slightly dierent, because the perturbed
eigenstate is not exactly the same as |
(0)
n
.
I Further shifts are given by the second and higher order corrections to
the energy.
Quantum mechanical perturbation theory
Lecture 4. Perturbation theory September 22 6 / 17
To obtain the rst-order correction to the energy eigenstate, we recall the
expression derived earlier
H
(0)
(1)
n
+
V
(0)
n
= E
(0)
n
(1)
n
+E
(1)
n
(0)
n
(8)
and multiply it by
(0)
m
, (m = n) from left and integrate. We obtain
(E
(0)
m
E
(0)
n
)
(0)
m
|
(1)
n
=
(0)
m
|V |
(0)
n
(9)
We expand |
(1)
n
as
|
(1)
n
=
m
a
m
|
(0)
m
(10)
When two above equations are combined, we obtain
|
(1)
n
=
m =n
(0)
m
|V |
(0)
n
E
(0)
n
E
(0)
m
|
(0)
m
(11)
The rst-order change in the n-th energy eigenfunction has a contribution
from each of the energy eigenstates m = n.
Quantum mechanical perturbation theory
Lecture 4. Perturbation theory September 22 7 / 17
The second order correction to the energy is
E
(2)
n
=
m =n
|
(0)
m
|V |
(0)
n
|
2
E
(0)
n
E
(0)
m
(12)
Conclusion:
I Each term is proportional to the matrix element
(0)
m
|V |
(0)
n
I This is a measure of how much the perturbation mixes eigenstate n
with eigenstate m
I It is also inversely proportional to the energy dierence between
eigenstates m and n, which means that the perturbation deforms the
eigenstate to a greater extent if there are more eigenstates at nearby
energies.
I Expression is singular if any of these states have the same energy as
state n, which is why we assumed that there is no degeneracy
I Higher-order deviations can be found by a similar procedure
MP perturbation theory
Lecture 4. Perturbation theory September 22 8 / 17
The MP-energy corrections are obtained with the perturbation (correlation
potential):
V = H F
0
| H F |
0
(13)
where H is the usual electronic Hamiltonian and the Slater determinant
0
is
the eigenfunction of the Fock-operator F
F
0
= 2(
N/2
i=1
i
)
0
(14)
where N is the number of electrons of the molecule under consideration and
i
is the orbital energy belonging to the doubly occupied spatial orbital. The
shifted Fock operator
H
0
= F +
0
| H F |
0
(15)
serves as unperturbed (zeroth-order) operator. The Slater determinant
0
being an eigenfunction of F, it follows that
H
0
0
=
0
| H|
0
0
(16)
MP perturbation theory
Lecture 4. Perturbation theory September 22 9 / 17
so that the zeroth-order energy is the expectation value of H with respect to
0
, i.e., the HartreeFock energy:
E
MP0
= E
HF
=
0
|H|
0
(17)
Since the rst-order MP energy
E
MP1
=
0
|
V |
0
= 0 (18)
is zero, the lowest-order MP correlation energy appears in second order. This
result is the MllerPlesset theorem: The correlation potential does not
contribute in rst-order to the exact electronic energy.
MP perturbation theory
Lecture 4. Perturbation theory September 22 10 / 17
In order to obtain the MP2 formula for a closed-shell molecule, the second
order formula is written on basis of doubly-excited Slater determinants
(singly-excited Slater determinants do not contribute, see Brillouin theorem).
After integrating out spin, it becomes
E
MP2
=
i,j,a,b
i
(1)
j
(2)|
1
r
12
|
a
(1)
b
(2)
2
a
(1)
b
(2)|
1
r
12
|
i
(1)
j
(2)
a
(1)
b
(2)|
1
r
12
|
j
(1)
i
(2)
i
+
j
a
b
(19)
where
i
and
j
are occupied orbitals and
a
and
b
are virtual (unoccupied)
orbitals. The quantities
i
,
j
,
a
, and
b
are the corresponding orbital
energies. Through second-order in the correlation potential, the total
electronic energy is given by the HartreeFock energy plus second-order MP
correction:
E = E
HF
+E
MP2
(20)
MP perturbation theory
Lecture 4. Perturbation theory September 22 11 / 17
Concluding remarks
I Systematic studies of MP perturbation theory have shown that it is not
necessarily a convergent theory at high orders. The convergence
properties can be slow, rapid, oscillatory, regular, highly erratic or simply
non-existent, depending on the precise chemical system or basis set.
I Various important molecular properties calculated at MP3 and MP4
level are in no way better than their MP2 counterparts, even for small
molecules.
I For open shell molecules, MPn-theory can directly be applied only to
unrestricted HartreeFock reference functions. However, the resulting
energies often suer from severe spin contamination, leading to very
wrong results. A much better alternative is to use one of the MP2-like
methods based on restricted open-shell HartreeFock references.
Example: Atomization energies
Lecture 4. Perturbation theory September 22 12 / 17
Table 1: Calculated and experimental electronic atomization energies (kJ/mol)
Molecule HF CCSD MP2 Exp.
F
2
-155.3 128.0 185.4 163.4
H
2
350.8 458.1 440.7 458.0
HF 405.7 583.9 613.8 593.2
H
2
O 652.3 960.2 996.1 975.3
O
3
-238.2 496.1 726.6 616.2
CO
2
1033.4 1573.6 1745.2 1632.5
C
2
H
4
1793.9 2328.9 2379.3 2359.8
CH
4
1374.1 1747.0 1753.1 1759.3
I Accuracy of the MP2 is satisfactory despite its relatively low
computational cost
I MP2 usually overestimates bond energies
Example: Reaction enthalpies
Lecture 4. Perturbation theory September 22 13 / 17
Table 2: Calculated and experimental electronic reaction enthalpies (kJ/mol)
Reaction CCSD MP2 Experiment
CO + H
2
CH
2
O -23.4 -25.0 -21.8
H
2
O + F
2
HOF + HF -123.3 -127.2 -129.4
N
2
+ 3H
2
2NH
3
-173.1 -164.4 -165.4
C
2
H
2
+ H
2
C
2
H
4
-209.7 -196.1 -203.9
CO
2
+ 4H
2
CH
4
+ 2H
2
O -261.3 -237.3 -245.3
2CH
2
C
2
H
4
-830.1 -897.7.9 -845.7
O
3
+ 3H
2
3H
2
O -1010.1 -939.7 -935.5
I The accuracy of MP2 is in the same level than CCSD
I It is problematic to improve MPPT calculations systematically
Review: Coupled Cluster method
Lecture 4. Perturbation theory September 22 14 / 17
I Coupled cluster (CC) method, especially The CCSD(T), has become
the gold-standard of quantum chemistry.
I The computatinal cost is very high. So, in practice, it is limited to
relatively small systems.
I It starts from the Hartree-Fock molecular orbital method and adds a
correction term to take into account electron correlation.
I Some of the most accurate calculations for small to medium sized
molecules use this method.
I A drawback of the method is that it is not variational
I The abbreviations for coupled-cluster methods begin with the letters
CC followed by S - for single, D - for double excitations, etc.
Hybrid coupled cluster CCSD(T)
Lecture 4. Perturbation theory September 22 15 / 17
I T in the brackets means perturbative triple excitations
I Is the most popular hybrid CC method
I For high precision work, the CCSD model is usually not accurate and
CCSDT model is too expensive
Example: Water molecule CCSD(T) calculations
I For OH distances less than 3.5
A, the CCSD(T) works well, giving
about 90% of the full CCSDT triples correction.
I The model breaks down at larger distances
I The unrestricted CCSD(T) (based on UHF reference) does not provide
good description of the dissociation process.
Example: Atomization energies
Lecture 4. Perturbation theory September 22 16 / 17
Table 3: Calculated and experimental electronic atomization energies (kJ/mol)
Molecule HF CCSD CCSD(T) Exp.
F
2
-155.3 128.0 161.1 163.4
H
2
350.8 458.1 458.1 458.0
HF 405.7 583.9 593.3 593.2
H
2
O 652.3 960.2 975.5 975.3
O
3
-238.2 496.1 605.5 616.2
CO
2
1033.4 1573.6 1633.2 1632.5
C
2
H
4
1793.9 2328.9 2360.8 2359.8
CH
4
1374.1 1747.0 1759.4 1759.3
I CCSD(T) calculations produce accurate results
I Only for most problematic systems (such as ozone) higher order
corrections are desirable
Example: Reaction enthalpies
Lecture 4. Perturbation theory September 22 17 / 17
Table 4: Calculated and experimental electronic reaction enthalpies (kJ/mol)
Reaction CCSD CCSD(T) Experiment
CO + H
2
CH
2
O -23.4 -23.0 -21.8
H
2
O + F
2
HOF + HF -123.3 -119.5 -129.4
N
2
+ 3H
2
2NH
3
-173.1 -165.5 -165.4
C
2
H
2
+ H
2
C
2
H
4
-209.7 -205.6 -203.9
CO
2
+ 4H
2
CH
4
+ 2H
2
O -261.3 -244.7 -245.3
2CH
2
C
2
H
4
-830.1 -844.9 -845.7
O
3
+ 3H
2
3H
2
O -1010.1 -946.6 -935.5
I CCSD(T) is generally an improvement over CCSD
I CCSD(T) models chemical reactions within chemical accuracy (4
kJ/mol)
