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Post HF Method - Sourav
Post HF Method - Sourav
Chemistry
Sourav Pal
National Chemical Laboratory
Pune- 411 008
General classification of theoretical chemistry
approaches:
1 N 2 (N) N (N)
Slater Determinant
EAB ( R AB) E A + E B
H H
2 N2 ( cA c B); antibonding MO
H 1s H 1s
1 N1( cA cB ); bonding MO
H H
The ground state wavefunction is:
1(1) 1 (1) Slater determinant with two electrons
0
1(2) 1 (2) in the bonding MO
cA c B
Covalent terms, two electrons shared between two AOs
cB c A
H2 Potential Energy Surface
E .
H + H . At the dissociation
0 limit, H2 must separate
into two neutral atoms.
H H
Bond stretching
H H
At the RHF level, the wavefunction, , is 50% ionic and 50% covalent at all
bond lengths. cA c A cA c B
cB c B cB c A
H2 does not dissociate correctly at the RHF level!!
Should be 100% covalent at large internuclear separations.
RHF dissociation problem has several consequences:
Energies for stretched bonds are too large. Affects transition state structures -
Ea are overestimated.
Equilibrium bond lengths are too short at the RHF level. (Potential well is too
steep.) HF method overbinds the molecule.
.
However, SCF procedures recover ~99% of the total electronic energy around
equilibrium.
But, even for small molecules such as H2, the remaining fraction of the energy - the
correlation energy - is ~110 kJ/mol, on the order of a chemical bond.
To overcome the RHF dissociation problem,
Use two-configurational trial function that is a combination
of 0 and 1
First, write a new wavefunction using the anti-bonding MO.
2 N2 ( cA c B); antibonding MO
a0 0 a11 a0 (11) a1 (2 2 )
(a0 a1)cA c A c B cB (a0 a1 )cA c B c B cA
Ionic terms Covalent terms
Three points:
1. As the bond is displaced from equilibrium, the coefficients (a0, a1) vary
until at large separations, a1 = -a0: Ionic terms disappear and the molecule
dissociates correctly into two neutral atoms. The above wave function is
an example of configuration interaction.
a0 HF ai i Multi-determinant wavefunction
i 1
9 b b b
a,b,c =
8 a a a,b a a
virtual MOs
7
6 c c,d
5 k k,l
4 i i i,j i i
3
i,j,k =
occupied MOs 2 j j j
1
HF Hartree Fock
Where occ virt
Cia ia
(1)
CI | H | CI
ECI Expectation value of He.
CI | CI
3. The choice of active space - occupied and virtual orbitals - is not always
obvious. (Chemical intuition and experience help.) Convergence may be
poor.
H
H
C C O+ O
H O O- O O
H
Singlet state of twisted zwitterionic biradical
ethene, biradical.
H
C N H H C N
C N
Transition State
Mller-Plesset Perturbation Theory
In perturbation theory, the solution to one problem is expressed in terms of
another one solved previously. The perturbation should be small in some
sense relative to the known problem.
H W
W W0 W1 W2 ...
0 1 2 As the perturbation is turned on, W (the
energy) and change. Use a Taylor series
00 11 22 ... expansion in .
and H '
Define H0
N
NN
H0 Fi hi J ij K ij
i 1
i1
j 1
Unperturbed H is the sum over Fock
operators Moller-Plesset (MP) pert th.
N N N N
H ' gij gij Perturbation is a two-electron
i 1 j 1 i 1 j 1 operator when H0 is the Fock
operator.
W0 sum over MO energies
With the choice of H0, the first
W = | H '| E(HF )
1 0| 0 contribution to the correlation
energy comes from double
occ vir 0| | H '| ab ab
ij | H '| 0
W2
ij
excitations.
i j a b E 0 E ijab
Because the computational effort is significanly less than CISD and the
size-extensivity, MP2 is a good method for including electron correlation.
Coupled Cluster Theory
Perturbation methods add all types of corrections, e.g., S,D,T,Q,..to a given
order (2nd, 3rd, 4th,).
Coupled cluster (CC) methods include all corrections of a given type to infinite
order.
1 2 1 3 1k
T
e 1T + T T T Exponential operator generates
2 6 k 0 k! excited Slater determinants
T
T T T T N Cluster Operator
1 2 3
N is the number of electrons
CC Theory cont.
occ vir
t a a
T1 0 i i
i a The T-operator acting on the HF reference
occ vir generates all ith excited Slater Determinants, e.g.
t ab ab
T doubles ijab.
2 0 ij ij
i j a b
tia
tab
ij
Expansion coefficients are called amplitudes; equivalent to
the ais in the general multi-determinant wavefunction.
HF ref.
1 2 1 T 3 T 1 T 2 1 T T 4
2 1 T
e 1 T1 T T T T
T
T T T
2
2 1 3 2 1
6 1 4 3 1
2 2 2 2 1 24 1
singles doubles triples Quadruple excitations
1 2
T Connected doubles
2
T
2 2 T1 2
T Dis-connected doubles
1
T 3 Connected triples, true triples
3
T 1 T
T
3 T T
T
2 1
6 1 2 1
Product Triples, disconnected triples
T 3
1
1 T 2
T4 T 3 T
1
2 2 T 4
True quadruples - four electrons interacting
1 1
T 2 T
2
T 4
2
2 1
24 1 T2
Product quadruples - two noninteracting pairs
T , T
T T 2, T 4 Product quadruples, and so on.
3 1 2 1 1
CC Theory cont.
If all cluster operators up to TN are included, the method yields energies that are
essentially equivalent to Full CI.
In practice, only the singles and doubles excitation operators are used forming
the Coupled Cluster Singles and Doubles model (CCSD).
e
T 1 T 2 T
1 T 2 T T
1T 1 T 3 1 T 2 1 T T 4
2 1 T
1 2 2 1 2 1 6 1 2 2 2 2 1 24 1
The result is that triple and quadruple excitations also enter into the energy
expression (not shown) via products of single and double amplitudes.
It has been shown that the connected triples term, T3, can be important. It can be
included perturbatively at a modest cost to yield the CCSD(T) model. With the
inclusion of connected triples, the CCSD(T) model yields energies close to the
Full CI in the given basis, a very accurate wavefunction.
Comparison of Models
HF << MP2 < CISD < MP4(SDQ) ~CCSD < MP4(SDTQ) < CCSD(T)
In cases where there is (a) strong multi-reference character and (b) for excited
states, MR-CI methods may be the best option.
Size-dependence
Dimer of non-interacting H2 molecules
D-CI wave function contains doubly excited
determinants on each H2 molecule , but not the
quadruply excited determinant
The product of monomer D CI, however, contains
the quadruply excited
ab x cd
However, exponential wave function of dimer
even at doubles level contains quadruply excited
determinant
MOLECULAR PROPERTIES
S. Pal, Phys. Rev A 39, 39, (1989); S. Pal, Int. J. Quantum Chem,
41, 443 (1992)
Fock Space Multi-reference Coupled-Cluster
Approach
( Mukherjee and Pal, Adv. Quant. Chem. 20, 291 ,1989)
A T (1) = B
Simplified expression
Y (I) = Z (I) A
K R Shamasundar and S. Pal, J. Chem. Phys. 114, 1981 (2001); Int. J. Mol. Sci.
3, 710 (2002)
Analytic linear response
Analytic linear response for FSMRCC
H(g) = H + gH(1)
n
J (Q ) C [An]C[ nA] H eff [ n ]
M [i ]
(T [i ] , H eff[i ] , [i ] )
i 0
E A ( C A[ n]C[ nA] 1)
)
[i ]
M [i ]
(T [i ]
,H ,
[i ]
eff
[i ] [i ]
| | c c | H H eff
[i ] [i ]
l
[i ]
l | [i ]
,l
| | | H H eff
[i ]
[i ] [i ] [i ] [i ]
| [i ]
,
Structure of FSMRCC response equations
n
M [k ]
k i T
[i ]
0
Structure of FSMRCC response equations
M n [k ]
C C
n [n]
A
[n]
A
0
k i H eff
i [i ]
Structure of FSMRCC response equations
M (k) depends on lower-valence Ts. Hence in the
stationary equation with respect to T[i] summation index is
from i to n , where n is the highest valence sector.
To solve Lagrange multipliers for a specific sector, all
higher valence s are necessary.
SEC decoupling, reverse to the T equations, is present in
the equations
In the [i] determining equation, all higher valence are
present and are in the inhomogeneous part of the equation
For the equation determining highest valence , the
inhomogeneous part contains model space coefficients and
this makes the theory state-specific
Structure of FSMRCC response equations
For the highest valence sector, the non-zero
inhomogeneous parts are present only for the closed parts
of (n)
Open and closed parts of are coupled in each FS sector
Closed part of Lagrange multipliers takes care of
incompleteness of model space
For incomplete model space, the closed parts appear
explicitly because effective Hamiltonian can not be
defined explicitly in terms of the cluster amplitudes
Similarity transformation approach can eliminate the
closed parts, but this is not available in general
Structure of FSMRCC response equations
Special case of incomplete model space/ complete model
space (CMS) results in simplifications. For CMS,
intermediate normalization makes the definition of the
effective Hamiltonian explicit, thus allowing definition of
closed parts of in terms of open amplitudes of , T and
model space coefficients
P H P = P Heff P = P Heff P
This the solution of amplitudes involves only the open
parts of them
Similar simplifications appear for quasi-complete model
space e.g. (1,1) Fock space
For (1,1) model space, the one-body part of (1,1) T and
amplitudes are not specifically required for energy
derivatives, since connected diagrams are not possible
using these operators.
Rigorous spectra and properties
Accurate calculation of difference energies using
multi-reference coupled-cluster method (accuracy
within 0.1mev)
Developed analytic approach based on variational
coupled cluster method for molecular properties of
closed and open shell molecules, excited states.
1( b1
1B 1
7.287 7.49b -76.0221 -0.636 -0.603 -0.712
3sa1)
(0.005 a.u.)
-76.0247
(0.00 a.u.)
-76.0284
(-0.005 a.u.)
1( b1
3B 1
6.878 7.0,c7.2d -76.0374 -0.520 -0.599 -0.478
3sa1)
(0.005 a.u.)
-76.0397
(0.00 a.u.)
-76.0426
(-0.005 a.u.)
Table II: Dipole moment values of the HCOO
radical using analytic Fock space multi-reference
coupled cluster response approach
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