Adiabatic Formalism

The Adiabatic Connection:
Generating DFT Functionals from

Coupled-Cluster Theory
Andrew M. Teale
CMA-CTCC workshop on computational

quantum mechanics
13th January 2009
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Wavefunction and DFT Approaches to the Electronic
Structure Problem
Wavefunction methods offer a systematic route to the

approximate solution of the electronic Schrödinger Equation
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Structure Problem

This means that in principle arbitrary accuracy can be
achieved, CCSD, CCSD(T), CCSDT, CCSDTQ, CCSDTQ5 ...
with good control of errors.
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Structure Problem

But they are expensive and have unfavourable scaling of the
cost with system size N 6 , N 7 ,N 8 ...
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Structure Problem

Density Functional Theory promises a way to circumvent this
problem - use simple model system with same electronic
density
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Structure Problem

Density Functional Theory promises a way to circumvent this
problem - use simple model system with same electronic
density
BUT, the model Hamiltonian associated with DFT contains a
contribution whose form is unknown - must be approximated.
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Structure Problem
The main disadvantage of DFT is that there is no systematic

route to the determination of this unknown contribution and
so the accuracy achieved is not easily controlled and can vary
from problem to problem
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Structure Problem

In a sense WFT and DFT are complementary - one has
systematic control of errors but high cost, the other has low
cost but uncontrolled errors.
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Structure Problem

In this talk we will examine the link between the two
approaches.
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Structure Problem

In this talk we will examine the link between the two
approaches.
To begin with we must briefly consider the Lieb formulation of
DFT
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The Generalized Lieb Formulation of DFT
Consider a generalized Hamiltonian of the form
X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i
the electronic interaction strength can be varied with the

parameter λ
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X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i

parameter λ
The ground state energy for an external potential v is
Eλ [v ] = inf Tr Ĥλ [v ]γ̂
γ̂→N
where the minimization is over all ensemble density matrices γ̂

containing N electrons
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X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i

parameter λ
The ground state energy for an external potential v is
Eλ [v ] = inf Tr Ĥλ [v ]γ̂
γ̂→N
where the minimization is over all ensemble density matrices γ̂

containing N electrons
Lieb established the mutual Legendre-Fenchel transforms for
the energy and universal functional
Z
Fλ [ρ] = sup Eλ [v ] − ρ(r)v (r) dr
v ∈X ∗
Z
Eλ [v ] = inf Fλ [ρ] + ρ(r)v (r) dr
ρ∈X
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The Lieb Formulation of DFT
The relationships between these conjugate functionals are the

Fenchel inequalities
Z
Fλ [ρ] ≥ Eλ [v ] − ρ(r)v (r) dr
Z
Eλ [v ] ≤ Fλ [ρ] + ρ(r)v (r) dr
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Z
Fλ [ρ] ≥ Eλ [v ] − ρ(r)v (r) dr
Z
Eλ [v ] ≤ Fλ [ρ] + ρ(r)v (r) dr
Providing that the potential v supports an N-electron ground

state the inequalities may be sharpened into an equality by
maximization wrt v or minimization wrt ρ
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Z
Fλ [ρ] ≥ Eλ [v ] − ρ(r)v (r) dr
Z
Eλ [v ] ≤ Fλ [ρ] + ρ(r)v (r) dr
Providing that the potential v supports an N-electron ground

state the inequalities may be sharpened into an equality by
maximization wrt v or minimization wrt ρ
So, given a potential v or density ρ for any interaction
strength λ we can determine its conjugate partner
E. H. Lieb, Int. J. Quant. Chem., 24, 243, (1983)
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The Adiabatic Connection
In terms of the generalized Hamiltonian
X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i
and the ensemble-density matrix γ̂ the universal Lieb

functional may then be written as
Fλ [ρ] = inf Tr Ĥλ [0]γ̂ = Tr Ĥλ [0]γ̂λρ
γ̂→ρ
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X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i

γ̂→ρ
This can be written in terms of the non-interacting functional

Z λ
dFλ [ρ]
Fλ [ρ] = F0 [ρ] + dλ
0 dλ
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X 1X 2 X 1 X
Ĥλ [v ] = T̂ + λŴ + v (ri ) = − ∇i + λ + v (ri )
2 rij
i i i>j i

γ̂→ρ
This can be written in terms of the non-interacting functional

Z λ
dFλ [ρ]
Fλ [ρ] = F0 [ρ] + dλ
0 dλ
Then applying the Hellmann-Feynman theorem
dFλ [ρ]
= Tr Ŵ γ̂λρ = Wλ [ρ]
dλ
Z λ
ρ
Fλ [ρ] = Tr Ĥ0 [0]γ̂0 + Wλ [ρ] dλ
0
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This may be written in the alternative form
Z λ
ρ
Fλ [ρ] = Tr Ĥλ [0]γ̂0 + Wc,λ [ρ] dλ, Wc,λ [ρ] = Wλ [ρ] − W0 [ρ]
0
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Z λ
ρ
0
Term 1 is the uncorrelated kinetic energy plus λ times the
coulomb and exchange contributions. Term 2 is the correlation
correction required upto the chosen interaction strength
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Z λ
ρ
0
Term 1 is the uncorrelated kinetic energy plus λ times the
coulomb and exchange contributions. Term 2 is the correlation
correction required upto the chosen interaction strength
The universal functional is then decomposed in the usual
manner
Fλ [ρ] = Ts [ρ] + λJ[ρ] + λEx [ρ] + Ec,λ [ρ]
Ts [ρ] = Tr Ĥ0 [0]γ̂0ρ = Tr T̂ γ̂0ρ = min Tr T̂ γ̂

γ̂→ρ
ZZ
−1
J[ρ] = ρ(r1 )ρ(r2 )r12 dr1 dr2
Ex [ρ] = W0 [ρ] − J[ρ]

Z λ
Ec,λ [ρ] = Wc,λ [ρ] dλ
0 8 / 28
Adiabatic Connection
We can also define a representation for the
exchange-correlation energy as
Wxc,λ [ρ] = Ex [ρ] + Wc,λ [ρ] = Wλ [ρ] − J[ρ]
Z λ
Exc,λ [ρ] = Wxc,λ [ρ] dλ
0
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Z λ
0
The correlation contribution to the kinetic energy may also be

determined via
Z λ
Tc,λ [ρ] = Ec,λ [ρ] − Wc,λ [ρ] = (Wc,µ [ρ] − Wc,λ [ρ]) dµ
0
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Z λ
0
The correlation contribution to the kinetic energy may also be

determined via
Z λ
Tc,λ [ρ] = Ec,λ [ρ] − Wc,λ [ρ] = (Wc,µ [ρ] − Wc,λ [ρ]) dµ
0
So we can obtain the unknown exchange–correlation and

correlation contributions via a coupling constant integration of
Wxc,λ [ρ] and Wc,λ [ρ]
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Adiabatic Connection - Geometrical View
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Calculation of Adiabatic Connection Curves
We typically choose CC wavefunctions and to begin with
determine the CC density at full interaction strength this is
then reproduced for all values of λ
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Our task is then to perform the maximization
Z
F̃λ [ρ] = max Ẽλ [v ] − ρ̃λ=1 (r)v (r)dr = max [Cλ [v ]]
v v
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Z
v v
To do this we choose the following form for v

X
v (r) = vext (r) + (1 − λ)vref (r) + bt gt (r)
t
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Z
v v

X
t
and use the known derivatives
Z
δCλ
= [ρ(r) − ρλ=1 (r)] gt (r)dr
δbt
ZZ
δρ(r)
Hut = gu (r0 )gt (r) drdr0
δv (r0 )
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Z
v v

X
t
and use the known derivatives
Z
δCλ
= [ρ(r) − ρλ=1 (r)] gt (r)dr
δbt
ZZ
δρ(r)
Hut = gu (r0 )gt (r) drdr0
δv (r0 )
Once maximized the potential is the conjugate partner of the
physical density, at a chosen interaction strength
11 / 28
Calculating Adiabatic Connections
A. M. Teale, S. Coriani and T. U. Helgaker, (accepted JCP)
12 / 28
Application to Two Electron Systems
Repeating the optimization many times allows us to build up
the AC curve. This allows us to determine Exc via
Z 1
Exc = Wxc,λ dλ
0
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Z 1
Exc = Wxc,λ dλ
0
This may be compared with
FCI
Exc = E FCI − Ts − J − Ene − Enn
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Z 1
Exc = Wxc,λ dλ
0
FCI
The Ts component is the only unknown part - this can be
obtained from maximizing C [v ] at λ = 0 since F0 = Ts .
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Z 1
Exc = Wxc,λ dλ
0
FCI
In two electron systems it is also the von Weizsäcker
expression (a simple functional of the FCI density)
|∇ρ(r)|
Z
1
Ts [ρ(r)] = dr
8 ρ(r)
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Z 1
Exc = Wxc,λ dλ
0
FCI
In two electron systems it is also the von Weizsäcker
expression (a simple functional of the FCI density)
|∇ρ(r)|
Z
1
Ts [ρ(r)] = dr
8 ρ(r)
To provide estimates of the basis set limit energies and AC
curves we apply basis set extrapolation techniques.
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Application to Two Electron Systems: The H2 Molecule
Recently there has been interest in studying the AC of the
prototypical H2 system
M. Fuchs, Y.-M. Niquet, X. Gonze, and K. Burke, J. Chem. Phys., 122, 094116, (2005)
M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

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The dissociation of this molecule is difficult to describe
properly in DFT

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properly in DFT
The correct ground state wavefunction is a singlet at all
internuclear separations R

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properly in DFT
This is consistent with ρα (r) = ρβ (r) = ρ(r)/2 and can be
enforced in spin restricted calculations

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properly in DFT
However this gives very poor dissociation energies - these can
be fixed by using a spin unrestricted formalism

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properly in DFT
BUT the success comes at a price - the spin densities now
localize so that α is on one side, and β is on the other !

14 / 28
properly in DFT
BUT the success comes at a price - the spin densities now
localize so that α is on one side, and β is on the other !
This is clearly unphysical at R = ∞ we should have two spin
unpolarized H atoms

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As the electron-electron interactions are switched on the

nature of the wavefunction changes from the KS single
determinant to the real electronic wavefuntion
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This is reflected in the one-electron density matrix. Although
the spatial density ρ(r) is fixed
17 / 28

The eigenvectors / eigenvalues of the reduced one-electron
density matrix are the natural orbitals / occupation numbers
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The eigenvectors / eigenvalues of the reduced one-electron
density matrix are the natural orbitals / occupation numbers
We can examine the occupation numbers as a function of
interaction strength to gauge how the wavefunction evolves
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The Modified External Potential
The potential was expanded as
vλ (r) = vext (r) + (1 − λ)vJ (r) + vxc,λ (r)
X
= vext (r) + (1 − λ)vref (r) + bt gt (r)
t
T. Heaton-Burgess, F. A. Bulat and W. Yang, Phy. Rev. Lett., 98, 256401, (2007)
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X
t
The exchange–correlation contribution is then

X
vxc,λ (r) = (1 − λ)[vref (r) − vJ (r)] + bt gt (r)
t
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X
t

X
t
For 2 electron systems we can also use vx (r) = − 21 vJ (r) to

get the correlation potential
(1 − λ)
vc,λ (r) = vxc,λ (r) + vJ (r)
2
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X
t

X
t
For 2 electron systems we can also use vx (r) = − 21 vJ (r) to

get the correlation potential
(1 − λ)
vJ (r)
vc,λ (r) = vxc,λ (r) +
2
Whilst the potentials may not be unique in a finite basis a
penalty function minimization can be performed to give
smooth potentials, changing Wλ by less than 10−5 a.u.
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The Modified External Potential: vxc,λ (r)
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The Modified External Potential: vc,λ (r)
C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)
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Building DFT Functionals Using the AC
The obvious motivation for studying the AC is to develop
improved Exc functionals.
A. D. Becke, J. Chem. Phys., 98, 1372, (1993)

M. Ernzerhof, Chem. Phys. Lett., 263, 499, (1996)
A. J. Cohen, P. Mori-Sánchez and W. Yang, J. Chem. Phys., 127, 034101, (2007)

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Simple forms for approximating Wλ can be turned directly
into Exc functionals by integration.


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This idea has been followed before,


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The Becke H&H funcitonal used linear interpolation with Ex
LDA for W
for the W0 and Exc 1


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LDA for W
Ernzerhof considered a Padé type form


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LDA for W
Mori-Sánchez, Cohen and Yang considered a variety of simple
forms


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LDA for W
Mori-Sánchez, Cohen and Yang considered a variety of simple
forms
We investigated a variety of forms for H2 and the Helium
Isoelectronic series with the input parameters determined from
FCI data.

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Two forms were found to give good performance for these two
electron systems; A Padé type form and an Exponential form.
M. J. G. Peach, A. M. Miller, A. M. Teale and D. J. Tozer, J. Chem. Phys., 129, 244104, (2008)
23 / 28
Two forms were found to give good performance for these two
electron systems; A Padé type form and an Exponential form.
The Padé type form is
AC1 = a + bλ
Wxc,λ
1 + cλ
AC1 c − loge (1 + c)
Exc =a+b
c2
a = Wxc,0 = Ex
0
b = Wxc,0 = EcGL2
0
Wxc,0
c = −1
Wxc,1 − Wxc,0
D E
Wxc,1 = Ψ1 Ŵ Ψ1 − J

23 / 28
The Exponential form is

AC6
Wxc,λ = a + b exp (cλ)
AC6 b
Exc (1 − exp (−c))
=a+
c
0
b(1 − exp(Wxc,0 /b)) = Wxc,0 − Wxc,1
a = Wxc,0 − b
0
Wxc,0
c =
b
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Potential Energy Curves of H2 from Approximate Forms
The potential energy curves for the H2 molecule determined
with accurate input parameters are
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Comparison with the Accurate Integrand
A. M. Teale, S. Coriani, and T. U. Helgaker (accepted, JCP)
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Conclusions
We can calculate AC curves corresponding to accurate

coupled cluster wavefunctions
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Conclusions

The resulting curves accurately reproduce the CC density and
the correct exchange–correlation energies
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Conclusions

The direct optimization approach provides a rapidly
convergent scheme, this is ensured by our calculation of the
second derivative
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Conclusions

second derivative
The curves provide the missing link between constrained
search methods which provide the Kohn-Sham potential but
no associated energy functional and approximate energy
functionals suitable for practical use
27 / 28
Conclusions

second derivative
The curves provide the missing link between constrained
search methods which provide the Kohn-Sham potential but
no associated energy functional and approximate energy
functionals suitable for practical use
The curves determined are useful for understanding
approximate exchange–correlation forms and the development
of new ones
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Acknowledgements
Trygve Helgaker Sonia Coriani
David Tozer Michael Peach
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Adiabatic Formalism

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The Adiabatic Connection:

Generating DFT Functionals from

CMA-CTCC workshop on computational

13th January 2009

Wavefunction methods offer a systematic route to the

Wavefunction methods offer a systematic route to the

Wavefunction methods offer a systematic route to the

Wavefunction methods offer a systematic route to the

Wavefunction methods offer a systematic route to the

The main disadvantage of DFT is that there is no systematic

The main disadvantage of DFT is that there is no systematic

The main disadvantage of DFT is that there is no systematic

The main disadvantage of DFT is that there is no systematic

the electronic interaction strength can be varied with the

the electronic interaction strength can be varied with the

where the minimization is over all ensemble density matrices γ̂

the electronic interaction strength can be varied with the

where the minimization is over all ensemble density matrices γ̂

The relationships between these conjugate functionals are the

The relationships between these conjugate functionals are the

Providing that the potential v supports an N-electron ground

The relationships between these conjugate functionals are the

Providing that the potential v supports an N-electron ground

and the ensemble-density matrix γ̂ the universal Lieb

and the ensemble-density matrix γ̂ the universal Lieb

This can be written in terms of the non-interacting functional

and the ensemble-density matrix γ̂ the universal Lieb

This can be written in terms of the non-interacting functional

Ts [ρ] = Tr Ĥ0 [0]γ̂0ρ = Tr T̂ γ̂0ρ = min Tr T̂ γ̂

Ex [ρ] = W0 [ρ] − J[ρ]

Wxc,λ [ρ] = Ex [ρ] + Wc,λ [ρ] = Wλ [ρ] − J[ρ]

Wxc,λ [ρ] = Ex [ρ] + Wc,λ [ρ] = Wλ [ρ] − J[ρ]

The correlation contribution to the kinetic energy may also be

Wxc,λ [ρ] = Ex [ρ] + Wc,λ [ρ] = Wλ [ρ] − J[ρ]

The correlation contribution to the kinetic energy may also be

So we can obtain the unknown exchange–correlation and

To do this we choose the following form for v

To do this we choose the following form for v

To do this we choose the following form for v

A. M. Teale, S. Coriani and T. U. Helgaker, (accepted JCP)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

M. J. G. Peach, A. M. Teale and D. J. Tozer, J. Chem. Phys., 126, 244104, (2007)

As the electron-electron interactions are switched on the

As the electron-electron interactions are switched on the

As the electron-electron interactions are switched on the

As the electron-electron interactions are switched on the

The exchange–correlation contribution is then

The exchange–correlation contribution is then

For 2 electron systems we can also use vx (r) = − 21 vJ (r) to

The exchange–correlation contribution is then

For 2 electron systems we can also use vx (r) = − 21 vJ (r) to

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)

C Umrigar and X Gonze, Phys. Rev. A, 58, 3827, (1994)