Non-local density functionals meet many-body dispersion:

A hybrid approach for van der Waals correlation

Jan Hermann, Matthias Schefer and Alexandre Tkatchenko
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
Many-body
dispersion
method
Mapping to oscillators The method starts
with projecting the response of valence elec-
trons onto a set of harmonic oscillators. It is
done by calculating volumes for the individu-
al atoms in a system and for corresponding free
atoms, and then renormalizing the free-atom
polarizabilities (response functions) using ratios
of these volumes.
=
V[n]
Vfree
,free
Screening polarizabilities In the next
step, the bare atomic response functions are
screened by neighboring atoms over the short-
range part of the dipole potential.
= T<R
Solving Schrdinger equation for cou-
pled oscillators In the last step, the MBD
correlation energy is calculated by exactly solv-
ing Hamiltonian for the coupled oscillators. For
this system, it is equivalent to doing RPA.

i
+
i

i +
i<j
i j

i j i T>R j
Local polarizability
formula
The use of renormalized free-atom polariz-
abilities brings problems for systems with
delocalized electrons (metals, ionic com-
pounds).
Atomic polarizabilities can be obtained
also directly from the electron density
employing the formula from Vydrovvan
Voorhis (VV) non-local functional.
(r, ) =
n

n + C

n
n

The only parameter C is related to a thresh-

old for the local electron gap, at which the
response of the electrons becomes efec-
tively damped.
The electron density partitioning is used
only as a computational tool in this ap-
proach, not as a physical model.
Works well for systems with strong ionic
character.
Getting the only parameter without
fitting
In the original formulation, parameter C
was obtained by ftting to empirical C co-
efcients (C = 0.0089).
We obtain it without any ftting using the
exact polarizability density of the hydro-
gen atom (C = 0.0094). See Fig. 1 for com-
parison.
Using density
gradient for short-
range screening
The polarizability screening step compli-
cates the MBD scheme and brings a sig-
nifcant technical disadvantage by compli-
cating derivation of analytical forces.
Short-range screening cannot be simply
skipped, it is important in semiconductors
or systems with strong resonance struc-
ture (hydrazoic acid below).
Summary & outlook
We present a synergy of interatomic
schemes, non-local functionals and ran-
dom-phase approximation by extending
the many-body dispersion method.
In the process, we get rid of dependence
on the free-atom data and lower sensitiv-
ity to the choice of electron density parti-
tioning.
In the future, we want to extend the local
polarizability model by introducing kinet-
ic energy density. This should efectively
cover delocalization efects (metals, reso-
nances).
Incorporate the model for dynamic polar-
izability from Perdew et al.
Employ the homogeneous electron gas as
a limiting case for construction of the in-
teraction dipole tensor.
Background
Simplest approach to treating van der Waals
interactions within density functional theory
(DFT) is to divide the molecular system into
atomic fragments and em-
ploy a pairwise approxima-
tion.
Several ways of deriving
the C coefcients exist, from simple empir-
ical schemes
1
to functionals of the electron
density.
2
A related, but alternative approach is the use
of non-local density functionals, two most
widely adopted families being vdW-DF
3
and
Vydrovvan Voorhis.
4
n(r)[n](r, r

)n(r

)drdr

Both the non-local functionals and the pair-

wise methods are essentially two-body for
long distances which is known to be invalid
for van der Waals interactions.
A popular approach to go beyond two-body
description is the random-phase approxima-
tion (RPA) used on top of a DFT calculation. It
is general and accurate, but brings a higher
computational cost.

n=

n
Tr[((r, r

, )v)
n
]
A way around this is to use RPA with approx-
imate response functions in the so-called
many-body dispersion (MBD) method.
5
Here, we link all these three approaches to-
gether while retaining their respective ad-
vantages.

i j
f (Ri j )
C,i j [n]
R

i j
References & info
1) S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys.
132, 154104 (2010).
2) A. Tkatchenko, M. Schefer, Phys. Rev. Lett. 102, 073005
(2009).
3) M. Dion, H. Rydberg, E. Schrder, D. C. Langreth, B. I.
Lundqvist, Phys. Rev. Lett. 92, 246401 (2004)
4) O. A. Vydrov, T. Van Voorhis, Phys. Rev. A 81, 062708
(2010)
5) A. Ambrosetti, A. M. Reilly, R. A. DiStasio, Jr., J. Chem.
Phys. 140, 18A508 (2014)
Contact: tkatchen@fhi-berlin.mpg.de
jhermann@fhi-berlin.mpg.de
(1) Local polarizability density in a hydrogen atom
(2) Two different dampings of van der Waals energy in rare gas dimers
The local polarizability approach has a po-
tential to overcome this problem because
its density-gradient dependence has the
capacity to cover the short-range screen-
ing efects.
atomic H(1) N(1) N(2) N(3)
renormalized 2.6 6.5 6.2 6.5
screened 2.1 7.3 5.4 7.1
VV 1.7 6.8 5.6 6.5
Diferentiation between the inner andout-
er nitrogen atoms is much higher for the
VV polarizabilities than for the bare renor-
malized polarizabilities.
Damping with xc
overlaps
ConnectingtheMBDenergy to theDFT en-
ergy requires damping, realized in a pair-
wise manner in construction of the dipole
interaction tensor.
Standard damping(such as Fermi-type be-
low) requires knowledge of the empirical
van der Waals radii and has no direct con-
nection to the underlying exchangecor-
relation (xc) functional.

+ expa
R
R
vdW
We overcome these issues by leveraging
atom pair overlaps of the (local) xc energy.
Ex/c[nA + nB] Ex/c[nA] Ex/c[nB]
Recovering van der Waals radii infor-
mation from correlation overlaps
Thesamelevel of information as contained
in the van der Waals radii can be recovered
from the overlaps as illustrated on the case
of rare gas atom dimers (Fig. 2).
We construct the damping simply from
the ratio of the correlation overlap to the
prototypical van der Waals atom pair en-
ergy C/R