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DMol

A Standard Tool for Density-Functional

Calculations
Jrg Behler
Fritz-Haber-Institut
der Max-Planck-Gesellschaft
Berlin, Germany
Bernard Delley
Paul-Scherrer-Institut,
Zrich, Switzerland
FHI Workshop 2003

Introduction
What is DMol3?
all-electron DFT-code
basis functions are localized atomic orbitals (LCAO)
can be applied to:
free atoms, molecules and clusters
solids and surfaces (slabs)

Topic of this talk

Characteristics of the DMol3 approach to DFT (selected aspects)

FHI Workshop 2003

History
DMol = density functional calculations on molecules

Main author:
Bernard Delley

Further contributions by:

J. Andzelm
J. Baker
G. Fitzgerald

R.D. King-Smith
D. Ellis
many more...

first fragments
early 1980s
(full potential electrostatics,
numerical atomic orbitals)
total energy functional
1983
electrostatics by partitioning
1986
first release of DMol by Biosym 1988
forces
1991
parallel version
1992
DSolid
1994
geometry optimization
1996
unification of DMol and DSolid
DMol3
1998
molecular dynamics
2002

FHI Workshop 2003

Localized Basis Sets

Why?
high accuracy (cusp, asymptotic behaviour)
high efficiency (few basis functions small matrix size)
What?
Gaussian type orbitals
(GTOs)
Slater type orbitals
(STOs)
numerical atomic orbitals (AOs)
Idea:
Most DFT codes use numerical integration (i.e. for XC-part)
in DMol3: numerical techniques used wherever possible
AOs can be used
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DMol3 Basis Functions

exact DFT-spherical-atomic orbitals of
neutral atoms
ions
hydrogenic atoms
radial functions are calculated in the setup (free atom)
implemented as numerically tabulated functions
Properties:
maximum of accuracy for a given basis set size
infinitely separated atoms limit treated exactly
small number of additional functions needed for
polarization
square integrability, cusp singularities at the nuclei
FHI Workshop 2003

Basis Set Example: Al

Atomic energy
minimal:
9 AOs

Al 1s, 2s, 2p, 3s, 3p E = -242.234806 Ha

dn:
13 AOs

Al2+ 3s, 3p

E = -242.234845 Ha

dnd:
18 AOs

z = 5 3d

E = -242.235603 Ha

dnp:
28 AOs

z = 4 3p, z = 7.5 4f

E = -242.235649 Ha

Quality test:
lowering of total energy by adding basis functions
(variational principle)
FHI Workshop 2003

Basis Set Example: Al

Radial Basis Functions
2.00

Al 1s

Radial Basis Function

1.50

Al 2s

1.00

Al 2p

0.50

Al 3s

0.00
-0.50

0.0

2.0

4.0

6.0

8.0

10.0

Al 3p

-1.00

Al+ 3s

-1.50

Al+ 3p

-2.00

3d z=5

-2.50

4f z=7.5

-3.00

3p z=4

r / bohr
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Basis Set Convergence

Atomic orbitals

Plane waves

basis set
rcut

quality
extension

Ecut
infinte

quality
extension

Basis test for the oxygen molecule

dnd
all

r
6

cut

/ bohr
10

11

12

13

14

15

-150.5570

O
O
O
O2+
O2+
z=3
z=5

-150.5575

E tot / Ha

O basis functions

-150.5580
-150.5585
-150.5590
-150.5595

1s
2s
2p
2s
2p
3d
3d

dnd all

-150.5600

FHI Workshop 2003

BSSE
Basis Set Superposition Error
Definition:
BSSE is a lowering of the energy when the electrons of
each atom spread into the basis functions provided by
the other atoms due to an incomplete basis set.
Plane waves: BSSE does not appear
GTO/STO Codes: BSSE can be a serious problem
DMol3: very small BSSE because of nearly perfect basis set
for the separated atoms limit
=> excellent description of weak bonds (but DFT limitation)
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Summary Basis Functions

Advantages
very efficient (small) basis fast calculations
allows for calculations without periodic boundary
conditions or less dense systems (slabs with large vacuum)
easy physical interpretation of basis functions
(almost) no basis set superposition error
different basis sets for different elements possible

Disadvantages
no systematic way to improve basis set quality
careful tests required to construct a basis set
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Numerical Integration
3 Step approach
1. Decomposition of the total integral in 3D into a sum of
independent integrals for atomic contributions
partitioning
2. Decomposition of each atomic integral into a radial
and an angular part spherical polar coordinates
3. Integration of the angular part on a sphere or
decomposition into separate integrations for and
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Partition Functions
1. Step: Decomposition into atomic contributions
Partition functions p are used to rewrite integrals over
all space:

f (r ) dr = f (r ) dr = f (r ) p (r ) dr

Sum of atomic integrals

f (r ) dr = f (r )dr

Enables integration using spherical polar coordinates!

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Partition Functions
Definition:
The partition function for a center :

g (r )
p (r ) =
g (r )

Normalization:

=1

choose one peaked function g for each center

Example:

calculate the partition function for each

center

Example:

g =
r

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Partition Functions
Total function:

Peaked functions gAand gB:

f
gA

gB

A B
-3

-2

-1

Partition functions:
1

pA

-2

-1

-2

-1

fA

B
0

fB

A
2

Decomposed functions:

pB

A
-3

-3

-3

-2

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-1

B
0

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Numerical Integration
Example: O atom
Radial Integration Meshes
8

Number of radial shells

n = s 14 ( z + 2 ) = 30
1
3

26
50
110
194
1

6
5
r / bohr

z = atomic number
s = scaling factor

points per shell

4
3
2
1
0
0

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10
20
shell number

30

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Numerical Integration
Example: O atom
Angular Integration Meshes
integration is done on Lebedev Spheres
integration scheme with octahedral symmetry

Order 7
26 points

Order 11
50 points

Order 17
110 points

Order 23
194 points

(projections of points on sphere into plane)

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Numerical Integration
Example: O atom (cutoff 10 bohr)
Total Grid:

Remarks:
user defined grids
higher order angular
schemes are possible
symmetry is used to reduce
number of points
a weight is assigned to each
point
in a molecule or solid a
superposition of atomic
meshes is used

3287 points

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Numerical Integration
Effect of mesh quality: total energy of the Al atom
cutoff radius / bohr

10

12

14

16

18

20

-6599.8

fine grid
coarse grid

E tot / eV

-6600.0
-6600.2
-6600.4
-6600.6
-6600.8

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Electrostatics
Classical electrostatic contribution in Hamiltonian
J [ ] =

1
(r1 ) (r2 )
dr1dr2

2
r12

Matrix elements
Hartee-Fock J
DFT

(r1 ) (r1 ) (r2 ) (r2 )

= P
dr1dr2
r12
=1 =1
L

(r1 ) (r1 ) (r2 )

=
dr1dr2
r12
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Electrostatics
Common procedure in DFT using localized basis functions:
Density-fitting using an auxiliary basis set { k }
auxiliary density

constraint

(r ) ~ (r ) = ck k (r )
k

~ (r ) dr = N

The basis functions { k } are of the same type as for the

wavefunction expansion.
Matrix elements
O(N3)

(r1 ) (r1 ) (r2 )

= ck
dr1dr2
r12
k

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Electrostatics
Approach to electrostatics in DMol3: Overview
Step 1

Partitioning: decompose the electron density into

atomic components

Step 2

Projection onto Ylm functions yields multipoles

attached to the atoms

Step 3

Solve Poissons equation for each multipole

(only 1-dimensional problem)

Step 4

Assemble electrostatic potential from all multipoles

and atoms
DMol3: No basis set required for density expansion!
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Electrostatics
1. Step: Partitioning of total density into atomic densities
like numerical integration
2. Step: Multipole expansion of each

lm (r ) =

1
4

1
Ylm ( , ) (r , , )dd

2l + 1
l max

(r , , ) 4 2l + 1lm (r )Ylm ( , )
lm

truncation of expansion at lmax

reduction to 1-dimensional radial density lm
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(r )
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Electrostatics
3. Step: Calculation of the potential contributions
Single center Poissons equation

2V (r , , ) = 4 (r , , )
1 1 l
=
2
2
r r r r
2

density
decomposition

= lm

spherical Laplacian

l max

1
V (r , , ) = Vlm (r )Ylm ( , )
lm r
potential expansion

set of equations for numerical evaluation of all

FHI Workshop 2003

Vlm (r )
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Electrostatics
4. Step: Construction of the total potential from
atomic contributions

V (r , , )
atomic mesh

(r )

full mesh

Calculation of the electrostatic potential: O(N2)

For periodic boundary conditions an
Ewald summation is included.
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Ewald Summation for

Monopoles
q

Positive Gaussians
Negative Gaussians

Background
charge
Point charges

Real space:

point charges + negative Gaussians

Reciprocal space:

background charge + positive Gaussians

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Extensions to
Ewald Summation
1. Generalization for lattices with multipoles
DMol3 contains an extension to lattices of point multipoles located at
the atomic sites:
applied to the lm
computationally as demanding as for point charge lattices

2. Extension to monopoles and multipoles of finite extent

Assumption: multipoles are located inside a radius rcut
Ewald terms with r < rcut have to be modified in the real space part,
because explicit calculation of the radial details of the extended
charge distribution is required.
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Electrostatics
Scaling (localized basis sets)
Hartree Fock

O(N4)

DFT in general

O(N3)

DMol3 molecular case

DMol3 solid case

O(N2)
O(N3/2)

Real systems:
O(N2)

Electrostatics in DMol3 scale almost

linearly with system size for large systems
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The Harris Functional

J. Harris, Phys. Rev B 31 (1985) 1770.
B. Delley et al., Phys. Rev B 27 (1983) 2132.

Kohn Sham energy functional

EKS [ ] = T [ ] + EH [ ] + E XC [ ] + Eext [ ] + Enn

Harris energy functional
N

E Harris [ ] = f i i EH [ ] + E XC [ ] XC [ ] d 3 r + Enn
i =1

Original idea of the Harris functional:

approximate DFT calculations for very large systems
non-selfconsistent energy calculation (1 iteration only)
approximated density = superposition of fragment densities (i.e. atomic
densities)
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Total Energy in

3
DMol

DMol3 uses the Harris functional (scf densities)

the Harris functional is stationary at the same density as the
Kohn-Sham functional and the two are equal in value at this
point
the curvature of EHarris about the stationary point is smaller
than the curvature of EKS
the density in the Harris functional does not have to be
V-representable

Reduction of numerical noise

Ebind = Etot E
Realization:

ref
atom

subtraction of atomic densities from total densities in

integrands
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More features ...

forces
geometry optimization
ab initio molecular dynamics and simulated annealing
COSMO (COnductor-like Screening MOdel )
transition state search
vibrational frequencies
Pulay (DIIS) charge density mixing
pseudopotentials (optional)

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Conclusion
Fast

very small basis sets, matrix diagonalization O(N3)

no costs for large vacuum or atom / molecules
efficient calculation of electrostatics
O(N) calculation of Hamilton and overlap matrix
Universal
atom, molecule and cluster calculations
solids and slabs with periodic boundary conditions
Accurate results
comparable to LAPW next talk
Easy to use
atoms are given in Cartesian coordinates
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References
Introduction:
B. Delley, J. Chem. Phys. 92 (1990) 508
B. Delley in Modern Density Functional Theory: A Tool for Chemistry,
Theoretical and Computational Chemistry Vol. 2, Ed. by J. M. Seminario
and P. Politzer, Elsevier 1995
B. Delley, J. Chem. Phys. 113 (2000) 7756
Further Details:
B. Delley, Comp. Mat. Sci. 17 (2000) 122
J. Baker, J. Andzelm, A. Scheiner, B. Delley, J. Chem. Phys. 101 (1994) 8894
B. Delley, J. Chem. Phys. 94 (1991) 7245
B. Delley, J. Comp. Chem. 17 (1996) 1152
B. Delley, Int. J. Quant. Chem. 69 (1998) 423
B. Delley, J. Phys. Chem. 100 (1996) 6107
B. Delley, M. Wrinn, H. P. Lthi, J. Chem. Phys. 100 (1994) 5785
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