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Transcript of The HIG of tdDFT - UCLAhelper.ipam.ucla.edu/publications/pltut/pltut_10579.pdf · IPAM HEDP Long...
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Sam Trickey
Quantum Theory Project Physics, Chemistry - University of Florida
IPAM HEDP Long Program Tutorial 16 March 2012
http://www.qtp.ufl.edu/ofdft [email protected]
©March 2012
The HIG of tdDFT
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Sam Trickey
The Highly Important Games of
Temperature-dependent DFT and Hartree-Fock
Quantum Theory Project Physics, Chemistry - University of Florida
IPAM HEDP Long Program Tutorial 16 March 2012
http://www.qtp.ufl.edu/ofdft [email protected]
©March 2012
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Funding: U.S. DoE DE-SC 0002139; CONACyT (México)
Collaborators (Orbital-free KE & FE functionals):
Jim Dufty (Univ. Florida)
Frank Harris (Univ. Utah and Univ. Florida)
Keith Runge (BWD Associates)
Tamás Gál (Univ. Florida)
Vivek Kapila (Univ. Arizona)
Valentin Karasiev (Univ. Florida)
Travis Sjostrom (Univ. Florida)
QTP
Collaborators (Materials and molecular calculations):
Jon Boettger (Los Alamos National Laboratory)
PUPIL (Joan Torras, Erik Deumens, Ben Roberts, Gustavo Seabra, Oscar Bertran)
deMon2k (Andreas Köster, Gerald Geudtner, Patrizia Calaminici, Carlos Quintanar, …)
Notker Rösch and company, TU München
Collaborators (XC functionals):
Klaus Capelle (IFSC, Univ. do ABC, Brazil)
José Luis Gázquez (UAM- I, México D.F.)
Alberto Vela (Cinvestav, México D.F.)
Victór Medel (Virginia Commonwealth Univ.)
Mariana Odashima (MPI Mikrostrukturphysik, Halle Germany)
Juan Pacheco Kato (Univ. Guanajuato, México)
Jorge Martín del Campo Ramirez (UAM- I, México D.F.)
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Challenge: Orbital-free functionals
Progress: New functionals, new reference calculations
Topics
QTP
Motivation: Physics of Warm Dense Matter: see M. Desjarlais on 12 Mar.
and F. Graziani on 13 Mar.
Survey
Problems of naïve variational theory (Zero T, finite T)
Implications for molecular dynamics on complicated materials
Density functional theory basics – Zero T, finite T
Finite-T Hartree-Fock
Open questions for WDM applications
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1 2( , , , )I I I Nm V R R R R
ion ionV E R R R
Molecular dynamics is a major simulation tool; See M. Murillo 14, 15 March.
MD implements Newton’s 2nd Principle:
Bottleneck: the potential. For electrons & ions, that
should be the Born-Oppenheimer free- energy
surface
WDM Systems and Simulation Bottleneck
QTP
Adapted from R. Redmer, LBNL WDM, 2011
H-He (8.6%) @ 1 Mbar, 4 kK
F({R}) is the electronic
free energy. Quantum Stat Mech
$ $ $ $ or € € € € € Quantum Stat Mech Box
WDM: NO small
parameters to do the QM!
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Challenge: Orbital-free functionals
Progress: New functionals, new reference calculations
Topics
QTP
Motivation: Physics of Warm Dense Matter: see M. Desjarlais on 12 Mar.
and F. Graziani on 13 Mar.
Survey
Problems of naïve variational theory (Zero T, finite T)
Implications for molecular dynamics on complicated systems
Density functional theory basics – Zero T, finite T
Finite-T Hartree-Fock
Open questions for WDM applications
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• The time-independent Schrödinger equation & Hamiltonian for the
Ne-electron problem with N fixed nuclei (Hartree atomic units):
Many-electron Quantum Mechanics
1 0 1 1 0 1 10;
,21 1
2 21
1 ,
12
1
ˆ , , , , ; , , , ;
1ˆ ,
: ,
e e e e e
e e e
e
e e
N N N N N
N N N N
IN i
i i I i ji I i j
N N
i i j
i i j
Z
h g
R R
R
r r r r R r r R
r rr R r r
r r r
The many-electron wave function is anti-symmetric on interchange of a pair:
0 1 1 0 1 1, , , , , ; , , , , , ;e e e ek k j j N N j j k k N N r r r r R r r r r R
Ne = number of electrons
N = number of nuclei
QTP
Sum of 1- & 2-body
Hamiltonians; symmetric
on interchange of a pair
Nuclear (ion) positions (Born-Oppenheimer approx.);
suppressed hereafter unless directly relevant.
2
1
1 E 27.2116 eV 1 au.=0.5292 Å
1One-electron KE: r2
electron electron
Hartree
m q
d
Hartree & traditional units:
2
2 / 2 1
1 E 13.6058 eV 1 au.=0.5292 Å
One-electron KE: r
electron electron
Rydberg
m q
d
Rydberg & traditional units:
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Why many-electron problem is tough; T=0 K Variational Principle
The variational principle
So why not just guess a trial wave function with a bunch of physically and
chemically plausible parameters and do the minimization calculation by brute
force numerical quadrature?
*
1
0 *
1
e
e
trial trial N
trial
trial trial N
d d
d d
r r
r r
*
*
1
0 0 0
* 0
( ) 0e
trial trial
trial trial N
trial
trial
H dr dr
H
Lagrange Multiplier to
preserve normalization
is equivalent to the Schrödinger equation. That is, the Schrödinger eqn. arises from requiring the first-order variation of Etrial to be zero:
QTP
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Approximate vs. exact wave functions:
HF is approx
0
1
2
ψ 1,2, , 1 2
1
1
2
2
trial e a b z e
A
B
b z e
a z e
N c N
c N
c N
All “excited” Slater
determinants
Full CI
Question 1: is this expansion exact? YES
Question 2: is this expansion rapidly converging? NO
Question 3: can the expansion be truncated and used as
a variational expression? Well YES; scheme is called MCSCF
(multi-configuration self-consistent field). But still have issues:
Selection of orbitals φ, parameters in them, … . Did we keep
the variation principle? Are we capturing the physics and
chemistry? Can we do the integrals? Credit: So Hirata
J.C. Slater (by SBT)
Examples, T=0 K Variational Principle
QTP
ψ 1,2, , 1 2trial e a b z eN N ↑Anti-symmetrizer
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ˆ1,2, , exp 1 2trial e a b z eN N T
Jastrow correlated wave function; much
used in Monte Carlo. Note: nodes are
fixed by the determinant. Explicit “r12”
dependence makes integrals difficult.
1,2, , ( ) 1 2trial e ij a b z e
i j
N f r N
1
1 1 1
† †
1
ˆe
j
j j j
Na a
i i a i a i
j
t a a a a
T
All possible orbital
substitutions
in the determinant
More examples, T=0 K Variational Principle
Coupled Cluster (CC) Ansatz ( single
reference). t- amplitudes are not
determined variationally in practice.
Keeping all substitutions through
doubles scales computationally as Ne6
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Why many-electron problem is tough; T=0 K Variational Principle
The variational principle
So why not just guess a trial wave function with a bunch of physically and
chemically plausible parameters and do the minimization calculation by brute
force numerical quadrature?
*
1
0 *
1
e
e
trial trial N
trial
trial trial N
d d
d d
r r
r r
*
*
1
0 0 0
* 0
( ) 0e
trial trial
trial trial N
trial
trial
H dr dr
H
Lagrange Multiplier to
preserve normalization
is equivalent to the Schrödinger equation. That is, the Schrödinger eqn. arises from requiring the first-order variation of Etrial to be zero:
QTP
Too many arbitrary forms, too many diverse parameterizations to guess,
too many parameters to vary, too many variables of integration!
Computational cost OK for one or a few molecules, NOT for Born-
Oppenheimer Molecular Dynamics
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For a normalized ground state, the energy is
*
0 0 1 0 1 1, , , ,e e eN N NH d d r r r r r r
2-particle reduced density matrix “2-RDM”
State function: anti-symmetric under particle exchange (Fermions!)
Hamiltonian: symmetric sum of 1- and 2-body interactions.
We end up doing integrals over all but one or two of the coordinates just to
eliminate them (change of variables), thus (introducing spin here):
1 1;0 01 1
2 2
0
0
(2)
0 1 1 1 1 1 2 1 2 1 2 1 2
(2) *
1 2 1 2 0 1 1 2 2 3 3 0 1 1 2 2 3 3 3
*
1 1 0 1 1 2 2 3 3
( ) | ( , ) |
1| : , , , , , , , ,
2
| : , , , ,
N e N e ee e
N
x xx x
x x
e e
N N N
e
h x x dx g x x x x dx dx
N Nx x x x dx dx
x x N
r r r
r r r r r r r r
r r r r 0 1 1 2 2 3 3, 2 3, , ,e e e ee
N N N Ndx dx dx r r r r
1-particle reduced density matrix “1-RDM”
Sum over spins
QTP
Why many-electron problem is tough; T=0 K Variational Principle
Guessing a 2-RDM and using it in the variational principle doesn’t work either.
This is the notorious N-representability problem: How can we know (NASC) that
a trial 2-RDM comes from a Ne -Fermion wave function? The answer is known
but using it is essentially as intractable as using the many-electron wave function.
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QTP
( ) ( )
( )
( ) ( )( )1
0
( ):
oneelementof complete set fermio
( ) ( ) l
n stat
n
( ) : ( (
s
) ; 1/ )
e
e e
e
e
e
e
d nN
N
ext B
N N
i i
i
N
i
N
e
p V Tr e
v
A A
k
Tr
N
T
r r r
r r
∣ ∣
Why many-electron problem is tough; T≠0 K
Grand canonical ensemble
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Challenge: Orbital-free functionals
Progress: New functionals, new reference calculations
Topics
QTP
Motivation: Physics of Warm Dense Matter: see M. Desjarlais on 12 Mar.
and F. Graziani on 13 Mar.
Survey
Problems of naïve variational theory (Zero T, finite T)
Implications for molecular dynamics on complicated materials
Density functional theory basics – Zero T, finite T
Finite-T Hartree-Fock
Open questions for WDM applications
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Hohenberg-Kohn Theorems – consider the Ne -electron Hamiltonian, which includes
an external potential (for us, the nuclear-electron attraction)
,
21 12 21
1 ,
1ˆ ,
ˆ ˆˆ ˆ ˆ ˆ:
e e e
e
N N N N
IN i
i i j i I i Ii j
ee ext ee Nuc electr
Z
Rr r
r Rr r
HK-I: “A given ground state density n0 (r) determines the ground state
wave function and hence all the ground state properties of an Ne -electron system.”
Original Proof: by contradiction [P. Hohenberg and W. Kohn, Phys. Rev. 136,
B864 (1964)
Modern Proof: Levy-Lieb constrained search (sequential application of the
Variational Principle, density by density)
[M. Levy, Proc. Natl. Acad. Sci. USA 76, 6062 (1979); L. Lieb, Internat. J. Quantum Chem.
24, 243 (1983)]
Density Functional Theory Rudiments
QTP
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DFT Rudiments: HK-I Proof by Contradiction
0ˆ ˆ,ext ext n
1. Consider a non-degenerate ground state. Suppose that there are two external
potentials that yield the same ground-state density:
2. Then by the variational principle
0 0 0 0 0 0 0
0 0 0
0 0
ˆ ˆ
ˆ ˆ
ext ext
ext ext
ext extd n v v
r r r r
3. But the argument can be done reversing primed and unprimed quantities.
This gives
0 0 ext extd n v v r r r r
4. Adding these last two results gives the contradiction 0 0 0 0
5. Therefore the ground state density determines the external potential and
hence, the ground state wave function.
Remark: this proof does not address the possibility of a density n which is
not associated with any vext (the v-representability problem)
QTP
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DFT Rudiments: HK Theorems & Equivalence Classes (Constrained Search)
Mel Levy’s idea: take all the wave-functions that give the same density and vary
over them first. Then vary the density. The variational expression becomes
*
1
*
0 1
*
1
1
min min ( )
min min ( ) ( )
e
etrial
etrial
trial trial N
trial trial ee trial Nn n
trial ee tri
Ne
Nal Nn n
e
d d
d d
d d v n d
r r
r r
r r r r r
Just a rewriting but establishes the Hohenberg-Kohn theorems
by constrained search.
QTP
HK-I: “A given ground state density n0 (r) determines the
ground state wave function and hence all the ground state
properties of an Ne -electron system.”
HK-II: “For such a system in an external potential vext(r), there
is a universal (i.e., independent of vext ) functional F[n] with
the following properties:
0
0 0( )
min
ext
ext ext
v
v
e
r
x
vn
tE n F n d n E
E n E E n
v
r r r
Mel Levy, Perdew Fest, Mar. 2008
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DFT Rudiments: HK-I Proof by Constrained Search ← blue heading means supplemental
2. Minimize this functional over all the Ne electron states that give n0
0
0
ˆ ˆmin
|
ee
n
r r r
E
3. Then at most 0 is a normalized linear combination of ground states, since
the external potential contribution to the total energy depends only on the
density:
0ext extd n v r r r
4. Therefore the ground state density determines the ground state wave function.
1. Consider the positive operator ˆ ˆee and form
ˆ ˆee E
Remarks: No v-representability problem, no restriction to non-degenerate
ground states. We have not shown that, subject to mild conditions, every density
is associated with at least one Ne electron state. In fact, there are infinitely many
such states for each density (Harriman, Phys. Rev. A 24, 680 (1981)).
QTP
| 1-particle reduced
density matrix
r r
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HK-II: “For an Ne –electron system with an external potential vext(r), there
exists a universal (i.e., independent of vext ) functional F[n] with the
following properties:
Original Proof: Essentially by announcement; the paper assumes that
HK-I holds for non-ground-state densities.
Modern Proof: Levy-Lieb Constrained Search
Form
DFT Rudiments : HK Theorems from Constrained Search (continued)
; ;ˆ ˆˆ ˆ: min ee min n ee min n
nF n
0 0 0 ; ;ˆ ˆˆ ˆ ˆ ˆ
:ext
ee ext min n ee ext min n
ext v
E
F n d n v E n
r r r
0
0 0( )
min physically acceptable ( )
ext
ext ext
v ext
v vn r
E n F n d n v E
E n E E n n
r r r
r
Then
which is the first piece of the theorem.
QTP
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Remark: This F[n] , the Levy functional, is NOT the same mathematical object as the
one originally defined by HK. In particular, there is no v-representability issue with
regard to the variation over n nor any restriction to non-degenerate ground state. This
functional does fulfill the role of the one defined by HK. It has its own problems
however. It is not convex and has some unpleasant functional derivative problems. For
most purposes, the Levy functional is good enough. See Lieb (1983).
Now apply the variational principle again
DFT Rudiments: HK-II proof (continued)
0 0
0 0
0 0 0 ; ;
0 0 ; ;
ˆ ˆˆ ˆ ˆ ˆ
ˆ ˆˆ ˆ
ee ext min n ee ext min n
ee min n ee min n
E
But the definition of min;n means that 0 0; ; 0 0
ˆ ˆˆ ˆmin n ee min n ee
Convexity: 1 2 1 2(1 ) [ ] (1 ) [ ]A an a n aA n a A n
QTP
0 0 0
0
0 0 ; ; 0 0
0 0 0 0
ˆ ˆ ˆˆ ˆ ˆ
ˆ ˆ [ ]ext
ee min n ee min n ee
ee v
F n
F n E n E
Taken together, these give bracketing inequalities
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0
0 0( )
min physically acceptable ( )
ext
ext ext
v ext
v vn r
e
E n F n d n v E
E n E E n n
d n N
r r r
r
r r
Recall HK-II
Do the variation with a Lagrange multiplier for fixed particle number
0ext e
ext
F n d n v d n N
Fv
n
r r r r r
rr
QTP
DFT Rudiments: Existence Thms and Proceeding Constructively (Kohn-Sham)
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DFT Rudiments: Existence Thms and Proceeding Constructively (Kohn-Sham)
The big challenge: HK-II says that F[n] exists but does not give a form that can
be used to do the variational problem just displayed.
But we do know how to form F[n] explicitly for a system of non-interacting
fermions with the same density set by some vKS as follows:
; ;
non-inter
non-inter ; ;
ˆ ˆˆ ˆ: min
ˆ ˆˆ 0 : min
KS
ee min n ee min nn
v KS
ee S min n min nn
F n
E n F n d n v
F n n
r r r
Non-interacting fermions means
min;n is a Slater determinant. ; 1
11, , det
! emin n e Ne
NN
*
1
1 1 1 2(2)
1 2 1 2
2 1 2 2
|
| |1| det
| |2
eN
SD j
j
SD SD
SD
SD SD
x x x x
x x x xx x x x
x x x x
The Slater determinant 1- and 2-RDMs are
So the KS kinetic energy is * 2
1
1[ ]
2
eN
s s j j
j
n n d x x
r
How is this useful?
QTP
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DFT Rudiments: Existence Theorems and Proceeding Constructively (cont’d.)
By definition, the non-interacting (independent particle) system must have energy
[ ]s S KSE n n d n v r r r
Again, do the variation with a Lagrange multiplier for fixed particle number
0S KS e
SKS
n d n v d n N
vn
r r r r r
rr
Choose the Lagrange multiplier to be the same as in the original system
by setting the zero of the potential vKS (adding a constant, if necessary).
So we may be able to map the problem into that of constructing vKS.
How can that be done?
Remark: v-representability of the ground-state density n0 has been
reintroduced as an assumption.
QTP
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21
2
1 21 2
1
. .
1 2
2
(depending on spins)
( ) ( )1
2
;
0 1,2
ext
F
v coul ext
S ee ext
S ee ext
S
quant chem
x c
j j
j
orrel S
xc
ee
N
j j
j
j
E n n E n E n
n E n E n
n E n E n
n n d
n nE
E n E n n n
E
n d d
n n
n
n
r r
r rr r
r r
r r
The non-interacting system becomes useful as follows. Rearrange the
interacting system functional as follows:
DFT Rudiments: Kohn-Sham Rearrangement
QTP
Lu Jeu Sham, Sanibel, 2010.
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What we have done is
0
xc
ext e
See ext
F n d n v d
E
n N
v vn n
r r r r r
r rr r
:extv ext S ee ext
S ee
xc
xc
EE n F n E n n E n E n
F n n E
n
E nn
Thus, the variation principle and Euler equation for the physical system become
S
KSvn
r
rComparison with the Euler Equation for the KS system
shows that
KS ee exx
tcE
v v vn
r r r
r
New task: construct Exc
QTP
DFT Rudiments: Details of the Kohn-Sham Construction -
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The Kohn-Sham equation (non-spin-polarized for simplicity) is:
221
2 2 1 1 1
1 1 2
( ); ;
R KSIxc j j j
I I
nZd v
rr r r R r R
r R r r
xcxc
Ev n
n
with the eXchange-Correlation potential given by
Remark: Exact exchange in DFT is defined by the KS determinant, NOT the
Hartree-Fock determinant.
Rudiments of K-S DFT
QTP
2
12
ˆ: min
the Kohn-Sham determinant
Sn
j j
j
n
n d
r r
Everything is known except for the XC functional EXC . It is known exactly
only in a few special cases.
Remark:
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xcxc
Ev n
n
1/3
constant original LDA, also
dimensionless functional of density
only later LDAs (Hedin-Lundqvist,
Perdew-Zunger, Vosko-Wilk-Nu
( ) [ ( )]
( ) ( ) [ ( )]
Rxc xcLDA
LDA
LDA
LDA
X
E n dr n U n
d n n F n
F
F
R
R
R R
r r
r r r r
ssair)
There are several classes of approximate functionals that
are demonstrably successful at different levels of prediction:
◊ Local Density Approximation
Rudiments of K-S DFT
QTP
◊ Generalized Gradient approximations add
terms dependent on density gradients:
1/3
2 1/3 4/3
( ) [ ( ), ( )]
( ) ( ) [ ( ), ( )]
( ) = 2(3 )
GGA
xc xcGGA
GGA
E n d n U n s
d n n F n s
s n n
R
R
R
R R
r r r r
r r r r r
r
a) FGGA determined by constraints, scaling inequalities, other exact
results: Perdew-Wang 91, Perdew-Burke- Ernzerhof, VMT, VT{84}
PBEmol, (Mexican DFT collaboration), etc.
b) FGGA determined in part by fitting to atomization energies: Becke etc.
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QTP
Free Energy Density Functional Theory
Eion-ion omitted for brevity.
1 2 21 1
.
2 2
1 22
1 2
.
1
[ ]
[ ]
: [ ]
: 1 ex
[ ] [ ]
p
( ) ( )1;
2
ionv coul ion
S s ee ion
S
S s ee ion
S j j j j
j j
ee
quant chem
x correl s
xc
n n E n E n T n
n T n E
E n E n n n T n
n E n
n T n E n E n
n d f d
n nE n d
n
n
d
r r r r
r rr r
r r
F
F
1 2 2
( ) ( )
: 1 exp
1/
ion ion
j j j j
j j
B
E n d n v
n f
k T
r r r
r r r
Mermin-Hohenberg-Kohn finite-temperature DFT
Basic equations are:
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1 2 2
: 1 exp
xcxc
j j j j
j j
v nn
n f
r r r
Otherwise the KS equations look the same as in the ground state.
K-S Free-energy DFT
QTP
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QTP
Thermal Hartree-Fock Approximation
The trace “Ne,SD” is over all Ne-electron Slater determinants Φ.
ˆ( ( ) ( ) )( , )1
0
21
2
( | ) ( ) ( )
( | ) ln Tr
[ ]
: ; [ ] : ln (1 ) ln(1 )
ee ione
e
HF
HF HF ion
H d v nN SD
HF
N
HF HF ee ex ion
HF j j HF B j j j j
j
d v n
e
T E E E n
f d k f f f f
r r r
r r r
r r
F
F T
T
* *
1 2 1 2
1 2
1 2
* *
1 1 2 2
1 2
1 2
1
( ) ( ) ( ) ( )1
2
( ) ( ) ( ) ( )1
2
: 1 exp ; : 1/
i j
j
i j i j
ee i j
ij
i j i j
ex i j
ij
j j B
E f f d d
E f f d d
f k T
r r r rr r
r r
r r r rr r
r r
Mermin [Ann. Phys. (NY) 21, 99 (1963)] proved that the Finite Temperature
Hartree-Fock approximation is the “obvious” generalization of ground-state
Hartree-Fock theory. Basic equations are:
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QTP
Thermal Hartree-Fock Approximation - continued
*
2 22
2
2
*
2 2
2
2
1
2
( ) ( )( ) ( ) ( ) ( )
( ) ( )( )
i j
j j
i i ion i j i
j
i j
j j
j
v f d
f d
r rr r r r r
r r
r rr r
r r
=
Variational minimization leads to the obvious generalization of the
ground-state HF equation:
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Challenge: Orbital-free functionals
Progress: New functionals, new reference calculations
Topics
QTP
Motivation: Physics of Warm Dense Matter: see M. Desjarlais on 12 Mar.
and F. Graziani on 13 Mar.
Survey
Problems of naïve variational theory (Zero T, finite T)
Implications for molecular dynamics on complicated materials
Density functional theory basics – Zero T, finite T
Finite-T Hartree-Fock
Open questions for WDM applications
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DFT for WDM – Major Open Questions
QTP
• Observation: OF-DFT may be necessary, not merely an attractive option for
WDM. Large numbers of small occupation numbers make the number of
MD steps comparatively small for conventional KS at finite T .
• Technical issue: pseudopotentials? (mean ionization state?)
[ , ] ?
[ , ] ln (1 ) ln(1 ) ?
[ , ] ?
s
s B j j j j
j
xc
n T
n T k f f f f
n T
T
• Temperature and density dependence of Fxc ?
• Implicit temperature dependence of ground-state Exc[n] used at finite T. Is Fxc [n, T]≈ Exc[n(T)] good enough?
• Same question for ground state OF-KE functionals: Ts[n,T] ≈ Ts[n(T)]?
• Orbital-free free-energy functionals in WDM regime -
Functional forms for tS [n, T] , sS [n,T] , uxc [n,T]?
Accurate ground-state limiting forms?
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Challenge: Orbital-free functionals
Progress: New functionals, new reference calculations
Topics
QTP
Motivation: Physics of Warm Dense Matter: see M. Desjarlais on 12 Mar.
and F. Graziani on 13 Mar.
Survey
Problems of naïve variational theory (Zero T, finite T)
Implications for molecular dynamics on complicated materials
Density functional theory basics – Zero T, finite T
Finite-T Hartree-Fock
Open questions for WDM applications
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• The KS eigenvalue problem is the high-cost computational step in B-O
MD. At every step:
2
; ; ;
2
; ;
for each configuration( ) ( ) | ( ) |
ˆ ( ) ( )
1ˆ ( ; )2
( ; ) ( ; ) ( ) ( )
k kk
KS
k k k
KS
KS
KS ion H xc
n f T
h
h v
v v v v
R R
R R R R
R
R R
r r R
r r
r R
r R r R r r
Too slow! Order NeM with 2.6 ≤ M ≤ 3 at best. Requires heroic calculations
(some of which have been done – need for the data is HIGH!)
There are “order-N” approximate methods but they are not general
(additional assumptions, e.g. about basis locality, etc., limit applicability).
B-O Forces from DFT
→ So there’s both urgency and opportunity for better methods. Or do we just
wait on bigger, faster machines?
QTP
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“Everyone knows Amdahl’s Law but quickly forgets it”
T.Puzak, IBM (2007)
QTP
1
(1 )
speedup; fraction parallel; number of processors
PP
N
P N
S
S =
99.9 % parallel, 2048 processors ,
speedup ≈ 675
IEE Computer, 41, 33 (2008)
Also see www.cs.wisc.edu/multifacet/papers/amdahl_multicore.ppt
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21
2 ( )
( )[ ( )]
[ , ] ln (1 ) ln(1 )
[ , ] [ ( ), ]
[ ( ), ]
k k
k
B k k k k
k
s
K
B
sS
s S
S
f T d
v
k f f f
nn
n T k f
n T d t n T
d s n T
r
r rr r
r r
T
T
The Ideal - Orbital-free DFT
With the K-S density kernels ts, sS and a good density-dependent (NOT orbital-dependent) FXC , DFT B-O forces would be simple:
Even at T=0, there are many well-known barriers to
getting ts , e.g., Teller non-binding theorem for Thomas-
Fermi-Dirac, failures of TF-von Weizsäcker, ….
L.H. Thomas,
Sanibel, 1975.
Photo by SBT
QTP
5/3 2 2/3
2
3(3 )
10
[ ] : , 0 1
[ ] : ( ) ,
( )1:
8
TF W TF W W W
TF TF TF
W
n
n c d n c
nn d
n
r r
rr
r
Scaled Thomas-
Fermi-von
Weiszäcker
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The Other KS Orbital Problem (Jacob’s Ladder)
Biblical (Genesis 28: 11-19)
William Blake, 1800; Also African-
American Spiritual (folk hymn)
• DFT – XC approximations
(John Perdew)
n LSDA
Hartree world
Heaven of chemical accuracy
n GGA
ts and/or 2n meta-GGA
x hyper-GGA
unocc. {φi} generalized RPA, etc.
Red = explicit orbital dependence
J. P. Perdew and K. Schmidt, in Density Functional
Theory and its Application to Materials,
V. Van Doren, C. Van Alsenoy, and P. Geerlings,
Eds., AIP, Melville, New York, 2001
Dilemma: “Everybody” is working on orbital-dependent XC functionals!
See Mexican Group work on “lower rung” XC functionals
QTP
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Here, in somewhat sloppy translationally invariant notation, is the basic
theme of the response function approach
2
(r) r (r - r ) (r ) (q) (q) (q)
(r )(r)(r - r ) r (q - q ) (q) (q,q )
(r ) (r )
[ (r)] (q - q ) (q) (q,q )
KS KS
KS KS
KS
KSs s
n d v n v
v vnd
v n n
v nn n n
Orbital-free KE Approaches – Response Function
Result is a set of non-local (two-point) approximations based on Average
Density Approximation, Weighted Density approximation, etc.
Various versions work moderately well for metals.
Another recent version works moderately well for insulators.
The non-locality is too complicated (computationally costly, introduces local
pseudo-potentials) for our purposes
QTP
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Orbital-free KE Approaches – Response Function
Density-dependent kernel for semiconductors C. Huang and E.A. Carter, Phys. Rev. B 81, 045206 (2010)
,
,
0
2
2 1/3
4/3
r r (r) (r ) r,r
(r,r ) : (r)(1 ) r-r
(3 )
80.65 0.89
3
s TF W
F
F
n
c d d n n w
w w k x
nk n x
n
QTP
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Introducing density-dependence in the kernel “… comes at the expense of
greatly complicating the derivation and making a straightforward numerical
implementation computationally expensive…” Y.A. Wang, N.Govind, and
E.A.Carter, Phys. Rev. B 60, 16350 (1999)
Two-point OFKE Functional Problems
QTP
Density-independent kernels suffer from nonlinear instability “ … in the sense
that the corresponding kinetic-energy functionals are not bounded from below.” X.
Blanc and E. Cancès, J. Chem. Phys. 122, 214106 (2005) N-representability issue?
Multiple parameters without physical constraints.
Different kernels for metals and semi-conductors: but what about pressure-
induced insulator-metal transitions?
Reference density is non-unique for bulk systems and undefined for finite ones.
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* 2
i
,
1r (r) (
[ ]
[ ] r [ (r)
[ ] [ ] [ ] [ ]
[ ] r [ (r)] (r) r (
)2
r
] r
)
ee xc ne
sI electronic I KS I I
i
s
e
is
n
S
E n E n E n E n
F E n d v n n d n
n
n
v
d t dn n
n
• Goal: a workable recipe for a one-point ts[n] purely for driving MD. Remember
the ground state formulation:
Orbital-free Density Functional Theory: Single-Point Strategy
• Obviously need analogous progress for T > 0 K: tS [n, T] , sS [n,T] , uxc [n,T]
• Observe: we do NOT seek a KE density kernel that will do everything that is in
the basic DFT theorems
• Assumption: continued progress on pure EXC approximations, i.e., not
hybrids or OEP (optimized effective potential).
QTP
• Desired: ts[n(r)] be no more complicated than GGA EXC (depends on gradient of
the density) or meta-GGA (depends on Laplacian of the density also).
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• Key Ingredient - Pauli KE, Pauli potential, and square root of density [M. Levy
and H. Ou-Yang, Phys. Rev. B 38, 625 (1988); A. Holas and N.H. March, Phys. Rev. A 44, 5521 (1991);
E.V. Ludeña, V.V. Karasiev, R. López-Boada, E. Valderama, and J. Maldonado, J. Comp. Chem. 20, 155
(1999) and references in these] An exact expression is
[ ] [ ] [ ], [ ] 0s Wn n n n
21(r) (r) (r) (r)
2
(r) 0 r
KSv v n n
v T n
Stationarity of variation with respect to density n yields
Single-point OF-KE Functional Construction
• Useful (but incorrect) clue: “Conjointness conjecture” [H. Lee, C. Lee, and R.G. Parr,
Phys. Rev. A 44, 768 (1991)]. The GGA EX is
4/3
2 1/3 4/3
[ ] r (r) (r)
(r) = 2(3 )
GGA
x x xE n c d n F s
s n n
• Conjointness:
5/3[ ] r (r) (r)
(r) (r)
GGA
s t
t x
n d n F s
F s F s
QTP
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SiO Stretch; Total energy vs.
bond length
All six Ts approximations fail to
bind! V violates positivity.
OF-DFT: Test of Existing Single-point (GGA) KE functionals
• Tests of 6 existing functionals, three
conjoint. KS density as input to each.
PW91: Lacks and Gordon, J.Chem.
Phys. 100, 4446 (1994) [conjoint]
PBE-TW: Tran and Wesolowski,
Internat. J. Quantum Chem. 89, 441
(2002) [conjoint]
GGA-Perdew: Perdew, Phys. Lett. A
165, 79 (1992) [conjoint]
DPK: DePristo and Kress, Phys. Rev. A
35, 438 (1987)
Thakkar: Thakkar, Phys. Rev. A 46,
6920 (1992)
SGA: Second order Gradient Approx. TS = TTF + (1/9) TW
J. Comput. Aided Matl. Design 13, 111 (2006)
QTP
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Parameterizations
• Tried two simple forms for modified enhancement factors. These forms would
be convenient for use in MD. No guarantee that any of these is optimal.
21
21
( ) 11
jN
PBE N
t j
j
sF s c
a s
2 21 2exp4
1 2(1 ) (1 )a s a s
tF C e C e
N=2 is typical PBE form as also used by Tran & Weslowski
N=3 is the form used by Adamo and Barone [J. Chem. Phys. 116, 5933 (2002)]
N=4 highest tried
• Constrain parameters to 0v
Initial parameterization used
(a) single SiO or
(b) SiO, H4SiO4, and H6Si2O7.
Stretched single Si-O bond in all cases with self-consistent KS densities.
OF-DFT: Modified conjoint KE functionals
QTP
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Single bond
stretching
gradient in
H2O.
OF-KE
parameters
from 3-member
training set
(SiO, H4SiO4,
and H6Si2O7)
except PBE2.
NO information
about H2O in
the set.
OF-DFT - Performance of Modified Conjoint, Positive-definite Functionals
All of our functionals give too large an equilibrium bond length.
QTP
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OF-DFT - Pauli Potentials Compared
Phys. Rev. B 80, 245120 (2009)
Comput. Phys. Commun. (submitted)
QTP
Pauli potential vθ , vicinity of the
Si site in SiO at R = 1.926 Å.
“KS” is the exact inversion from
the KS solution.
“GGA” is the Tran -Wesolowski
potential.
“mcGGA” is our PBE2 modified
conjoint-form (positivity
enforced).
TF+vW and scaled TF+vW/9 for
comparison.
PROBLEM:
mcGGA Pauli potential vθ singularities at the nuclei. TOO positive!
GGA goes negative. TF+vW/9 does too but TF+vW doesn’t ⇒ any
answer you want with TF+λvW!
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Beware of scaled Thomas-Fermi-von Weiszäcker used variationally in
OF-DFT, or even with the actual KS n0 (for a given XC) as
input, can lead to weirdness:
Paul Ayers (Sanibel 2007): “An ab initio quantum chemist will
wonder- “Is an N-representability constraint missing?”
Orbital-free KE – Problems with Simple Approaches
“If so, should we surrender? N-representability problems are very
difficult ….”
Functional
(all simple LDA XC) Etotal (Hartree)
TFλW, λW = 1 -85.734
TFλW, λW = 1/5 -128.801
TFλW, λW = 1/9 -139.887
KS (13s8p GTO) -127.484
TFλW from G. Chan, A. Cohen, and
N. Handy, J. Chem. Phys. 114, 631
(2001)
QTP
[ ]
[ ] [ ] [
[ ]
]
TFW
ee xc
TF W
ne
E n
E n E n E
n
n
0, 0,[ ] [ ]TF W TF W KS KSE n E n
[ ]:TF W TF W Wn
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Singularities are not fatal.
Left: Bcc Li lattice constant; Right fcc Al lattice
constant. mcGGA is our PBE-2,
parameterized to SiO implemented in modified
PROFESS code. GGA=Tran-Wesołowski
QTP
Are Positive Singularities Fatal to mcGGA?
Comput. Phys. Commun. (submitted)
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Solving the OFKE Euler equation with a KS code?
QTP
[ ] [ ] [ ], [ ] 0s Wn n n n
Why did we switch to the PROFESS code?
21(r) (r) (r) (r)
2
(r) 0 r
KSv v n n
v n
Chan, Cohen, and Handy
J. Chem. Phys. 114, 631
(2001)
Levy, Perdew, and
Sahni, Phys. Rev. A 30,
2745 (1984)
Stationarity of variation with respect to density n yields
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QTP
TFDvW, λW = 1
Etotal (Hartree)
Chan, Cohen
& Handy
Numerical KS
code
GTO KS
code
H atom -0.2618 -0.26183 -0.25997
Li atom -4.1054 -4.10542 -4.09635
Ne atom -85.7343 -85.73445 -85.73004
Solving the OFKE Euler equation with a KS code?
However, with simple linear mixing of densities and
starting from the pure von Weizsäcker KE, the
iterative convergence is very slow and unpredictable
Even a numerical grid diatomic molecule code is
slow to converge and unpredictable.
Comput. Phys. Commun. (submitted)
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Current work is to remove mcGGA singularities by partial resummation of
gradient expansion to respect Kato cusp condition. One functional has
been explored a little.
OF-DFT - Removing Pauli Potential Singularities
Phys. Rev. B 80, 245120 (2009)
H2O molecular total energy
as function of one bond
KS = reference calc (source of
input density; middle curve)
DPK = DePristo-Kress OFKE
functional reparameterized
for this case (2nd from top)
MGGA = meta-GGA functional of
Perdew and Constantin (top) Phys. Rev. B 75, 155109 (2007).
Thakkar functional (lowest curve)
RDA = This work (second lowest)
QTP
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• The model problem is a hard-walled rectangular parallelepiped
containing a few (1-8 for now) hydrogen atoms.
• Initial exploration with cubic box, edge-length L.
• A few fixed atomic positions are sampled.
• Box size is from 1 au3 (L = 1 au) to free-system limit (L → ∞).
• Temperature range: 0 ≤ T ≤ 200,000 K.
QTP
Confined System – finite-T Hartree-Fock
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Requirements:
• Match boundary conditions.
• Represent ground state and sufficient number of excited states at
different box sizes.
• Allow for efficient calculation of 2-electron integrals.
Basis:
Cartesian Gaussians truncated to
match BCs.
Coefficients a0 , aL set by requiring
each basis function to be continuous.
QTP
Basis Set – Confined System
0 0( ) : ( ; ) 0
: ( ; )x
n n
box c c
n
L c L c x
g x a g x x x x
a g x x x x L
0 (0) ; : ( ):x
n n
L xg g L 2( )
( ; ) ( ) cx xn n
c cg x x x x e
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Technical issues and resolution:
• Continuity of first derivative at matching point and corrections to
piecewise evaluation of KE matrix elements – works with a non-zero
piece-wise correction for p-type functions
• Efficient calculation of 2- electron integrals – finite-range integrals of
Gaussians and error functions done analytically as much as possible,
rest via Gauss-Legendre quadrature.
QTP
Basis Set - continued
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The ion configuration. Each ion is at the center of its own octant.
(An initial choice for exploration. In general, the ion configuration
is arbitrary.)
QTP
Results – 8 Atom Array of Cubical Symmetry in a Cubical Box
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Comparison of Exchange Functionals
QTP
Ex from finite-temperature Hartree-Fock (FTHF)
Ex from ground state LDA with FTHF density
Ex from temperature-dependent LDA (Perrot & Dharma-Wardana 1984
parameterization) with FTHF density.
All for 8 atoms, cubic symmetry, in cubic box, L = 6 bohr
Phys. Rev. B 85, 045125 (2012)
3 2 4/3( ) 3 3 4 ( , )/xE T d n T r r
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QTP
8 Atom Cubical Array – Low-T plateaus?
Fermi distribution for a single spin for four temperatures at L = 6 bohr.
Note that the T=0 K occupied orbitals induced by cubic symmetry are a
single a1g and a triply degenerate t1u.
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Finite-T Hartree-Fock, LDAx, LDAx(T) Exchange free energy
Periodic bcc Lithium at ambient and 2x density. Modified AbInit code.
(orbital-dependent, nor orbital free).
∆FX(T) = FX(T) - FX(T =100 K) per atom.
LDAx(T) is from Perrot and Dharma-Wardana, Phys. Rev. A 30, 2619 (1984).
QTP
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Finite-temperature Hartree-Fock, LDAx, LDAx(T) Total free energy
∆Ftotal(T) = Ftotal(T) - Ftotal(T= 100 K) per atom.
LDAx(T) is from Perrot and Dharma-Wardana, Phys. Rev. A 30, 2619 (1984).
QTP
Periodic bcc Lithium at ambient and 2x density.
Modified AbInit code (orbital dependent, not orbital-free).
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Finite-temperature Hartree-Fock, LDAx, LDAx(T) Eq. of State: ρ=0.6 g/cm3
Pressure vs T: HF, LDAx, LDAx(T)
∆P(T) = PHF(T) - PLDAx(T);
∆P(T) = PLDAx(T) (T) - PLDAx(T)
QTP
Bcc Lithium at ambient density. Modified AbInit
code (orbital dependent, not orbital-free).
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Pressure vs T: HF, LDAx, LDAx(T)
∆P(T) = PHF(T) - PLDAx(T);
∆P(T) = PLDAx(T) (T) - PLDAx(T)
Finite-temperature Hartree-Fock, LDAx, LDAx(T) Eq. of State: ρ=1.2 g/cm3
Bcc Lithium at 2 x ambient density. Modified AbInit code
(orbital-dependent, not orbital-free.
QTP
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• “Finite Temperature Scaling, Bounds, and Inequalities for the Noninteracting Density Functionals”,
J.W. Dufty and S. B. Trickey, Phys. Rev. B 84, 125118 (2011)
• “Positivity Constraints and Information-theoretical Kinetic Energy Functionals”, S.B. Trickey, V.V.
Karasiev, and A. Vela, Phys. Rev. B 84, 075146 [7 pp] (2011).
• “Temperature-Dependent Behavior of Confined Many-electron Systems in the Hartree-Fock
Approximation”, T. Sjostrom, F.E. Harris, and S.B. Trickey, Phys. Rev. B 85, 045125 (2012)
• “Issues and Challenges in Orbital-free Density Functional Calculations”, V.V. Karasiev and S.B.
Trickey, Comput. Phys. Commun. [submitted]
• “Comparison of Density Functional Approximations and the Finite-temperature Hartree-Fock
Approximation for Warm Dense Lithium”, V.V. Karasiev, T. Sjostrom, and S.B. Trickey, in
preparation
• “Constraint-based, Single-point Approximate Kinetic Energy Functionals”, V.V. Karasiev, R.S.
Jones, S.B. Trickey, and F.E. Harris, Phys. Rev. B 80 245120 (2009)
• “Conditions on the Kohn-Sham Kinetic Energy and Associated Density”, S.B. Trickey, V.V. Karasiev,
and R.S. Jones, Internat. J. Quantum Chem.109, 2943 (2009)
• “Recent Advances in Developing Orbital-free Kinetic Energy Functionals”, V.V. Karasiev, R.S. Jones,
S.B. Trickey, and F.E. Harris, in New Developments in Quantum Chemistry, J.L. Paz and A.J.
Hernández eds. [Research Signposts, 2009] 25-54
• “Born-Oppenheimer Interatomic Forces from Simple, Local Kinetic Energy Density Functionals”,
V.V. Karasiev, S.B. Trickey, and F.E. Harris, J. Computer-Aided Mat. Design, 13, 111-129 (2006)
References – OF-KE and thermal DFT
QTP
http://www.qtp.ufl.edu/ofdft
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“Improved Constraint Satisfaction in a Simple GGA Exchange Functional ”, A. Vela, J. Pacheco Kato,
J.L. Gázquez, J. Martín del Campo, and S.B. Trickey, J. Chem. Phys. [accepted]
“Non-empirical Improvement of PBE and Its Hybrid PBE0 for General Description of Molecular
Properties”
J.M. del Campo, J.L. Gázquez, S.B. Trickey, and A. Vela, J. Chem. Phys. [accepted]
“A new meta-GGA Exchange Functional Based on an Improved Constraint-based GGA”
J.M. del Campo, J.L. Gázquez, S.B. Trickey, and A. Vela, Chem. Phys. Lett. [submitted]
“Structure –dependence of the Magnetic Moment in Small Paladium Clusters: Surprising Results
from the M06-L Meta-GGA Functional”, R. Koitz, T.M. Soini, A. Genest, S.B. Trickey, and N. Rösch,
Internat. J. Quantum Chem. 112, 113-120 (2012)
“Variable Lieb-Oxford Bound Satisfaction in a Generalized Gradient Exchange-Correlation
Functional”, A. Vela, V. Medel, and S.B. Trickey, J. Chem. Phys. 130, 244103 (2009)
“Tightened Lieb-Oxford Bound for Systems of Fixed Particle Number”,
M. M. Odashima, K. Capelle, and S.B. Trickey, J. Chem. Theory and Comput. 5, 798 (2009).
References – better XC functionals
QTP
http://www.qtp.ufl.edu/ofdft