DCACPs

Dispersion Correcting Atom Centered
Potentials (DCACP) and Many-Body

Dispersion (MBD) contributions to interatomic
vdW forces
O. Anatole von Lilienfeld

Current: Argonne Leadership Computing Facility
From 2013: Chemistry Department, Basel University
Overview
Introduction
Why do we care?
What's the problem with vdW?
Atom-Electron approach (DCACP)
Motivation
First attempts
Applications
Atom-Atom approach (MBD)
Many-body dispersion in DFT
3-body dispersion effects
Many-body dispersion effects
Why do we care?
``There is plenty of room at the bottom'' (Feynman)

Intermolecular bonds are weaker than chemical bond, yet
crucial for many highly relevant processes
Self-assembly
Supra-molecular
Adhesion, adsorption, physisorption
Liquid phase (Solid covalent, Gas ideal)
Nano- and meso-scale objects
Soft matter
Biological systems
Why do we care?
Papers by D. Andrienko et al,

OAvL & Andrienko, JCP (2007)
Why do we care?
Low-dimensional systems
Supra-molecular systems,
liquids, and solids
Hybrid organic/inorganic
interfaces
Physico-chemical
Properties and reactions
Ionic
systems
Metals, alloys,
Semi-conductors, defects
Why do we care? compound design

Science (1991)
Many more
Norskov et al (Stanford/DTU)
Curtarolo&Beratan&Yang (Duke)
Ceder (MIT)
Wolverton (Northwestern)
Zunger (NREL)
Yamashita (UT)
von Lilienfeld (ANL)
A Franceschetti & A Zunger, Nature (1999)
Ar
Ar

vdW-DFT: Non-local functionals (depend explicitly on r and r') (Dion,
Langreth, Lundqvist et al. PRL (2004)).
SAPT-DFT: Explicit energy expansion for weakly interacting moieties

(Jeziorski, Szalewicz, Podeszwa et al. CR (1994), Hesselmann,
Jansen)
Empirical density functionals (Truhlar et al. JCP (2006), Goddard

PNAS (2004), ...)
Empirical atom centered potentials (von Lilienfeld, Tavernelli,

Roethlisberger, Sebastiani PRL (2004), DiLabio CPL (2008))
Interatomic (pairwise or beyond) dispersion corrections

Ahlrichs, Scoles et al (70's and 80's); Elstner, Hobza, Frauenheim,
Kaxiras et al (2001); Wu and Yang JCP (2002); Grimme J. Comp.
Chem. (2004,2006); Johnson and Becke JCP (2005-2007); Silvestrelli
PRL (2008); Tkatchenko and Scheffler PRL (2009); and others ...

Langreth-Lundqvist functional
Dion, Rydberg, Schroeder, Langreth, Lundqvist, PRL (2004).

Lee, Murray, Kong, Lundqvist, Langreth, PRB (2010).

Langreth-Lundqvist functional (vdW-DF-04 and vdW-DF-10)
vdW-DF-04
vdW-DF-10
Exchange: revPBE
Exchange: PW86
Local corr.: LDA
Local corr.: LDA
No free parameters
2 parameters
C6 error: ~ 20%
C6 error: ~ 60%(*)
(*) Vydrov and van Voorhis, PRA (2010).
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
Dispersion corrected atom

centered potentials (DCACP)
Motivation
General idea
electron-electron
atom-atom
atom-electron
Feynman, Phys Rev (1939)
Motivation
General idea
electron-electron
atom-atom
atom-electron
Motivation

R
Motivation

R
1/R7
Motivation
Add atom centered potential to external potential in SCF
Act weakly on electrons in outer low density regions
Atom-electron corrections not unusual in solid state

physics
relativistic effects for heavy atoms
DFT+U
dispersion corrected atom centered potentials

(DCACP) in 2004
self-interaction correction (Pollmann (2006))
band-gap correction (van de Walle (2007))
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
First attempts
von Lilienfeld, Tavernelli, Sebastiani, Roethlisberger, PRL (2004)
First attempts
von Lilienfeld, Tavernelli, Sebastiani, Roethlisberger, PRL (2004);

von Lilienfeld et al, PRB (2005)
DCACP applications
Tapavizca, Lin, von Lilienfeld, Tavernelli, Coutinho-Neto, Roethlisberger, JCTC (2007)
DCACP applications
Lin, von Lilienfeld, Coutinho-Neto, Tavernelli, Roethlisberger, JCPA (2007)
DCACP applications
Roethlisberger group: http://lcbcpc21.epfl.ch/DCACP/DCACP.html
DCACP applications
Tavernelli et al, Phys Rev B (2009)
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
Pair-wise corrected DFT

A
RAB
Tkatchenko & von Lilienfeld, PRB (2008)
r1
Coulomb
Screening
RAB
r2
Many-body
vdW Energy
Many-body
vdW Energy
Many-body
vdW Energy
Many-body
vdW Energy

For rare gas crystals, experimental
MBC estimated to be up to 10% of cohesive energy
Many-body
vdW Energy
Functional
MBC
LDA
35 %
PBE
50 %
TPSS
80 %
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
Many-body
vdW Energy
von Lilienfeld & Tkatchenko, JCP (2010)
Tkatchenko&Scheffler, PRL (2009)
Many-body
vdW Energy

Damping according to Tang&Toennis
Tkatchenko&Scheffler, PRL (2009)
Many-body
vdW Energy
Many-body
vdW Energy
Many-body
vdW Energy
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
Many-body
vdW Energy
Tkatchenko, von Lilienfeld, DiStasio, accepted in PNAS (2012)
r1
Coulomb
Screening
RAB
r2
Many-body
vdW Energy
Use DFT+MBD method
A. Tkatchenko, R. A. DiStasio Jr., R. Car, M. Scheffler, PRL (2012).
TS-vdW method
Self-consistent electrostatic screening (SCS)
Many-body vdW energy for a system of

coupled oscillators (CFDM)

SCS: Polarization and anisotropy in H6
TS-vdW:
+SCS:
LR-CCSD:
C6
C6
C6iso
166
89
115
161
692
638
165
223
238
(Reference)
All values in HartreeBohr6

C6 coefficients: from small to large silicon clusters
27% error
TDLDA: S. Botti et al., PRB (2008)
PBE(0)+MBD: S22 database

PBE+vdW
PBE+MBD
PBE0+MBD
MARE
PBE+vdW
9.1%
PBE+MBD
5.4%
PBE0+MBD
4.2%
S22 CCSD(T): Jurecka, Sponer, Cerny, Hobza, PCCP (2006); Sherrill et al., JCP (2010).

Important features of DFT+MBD
A
B
Seamless treatment of short-range (quantum) and long-range (classical)

screening
Models anisotropy, polarization, and depolarization for non-metallic molecules and
solids
Computes many-body dipole vdW energy to infinite order with a single parameter
Negligible computational cost compared to DFT (MBD calculation takes 1 min. for
1000 atoms on 1 processor)
Many-body
vdW Energy

Many-body vdW effects at play: Benzene molecular crystal
PBE+vdW
690 meV/molecule
PBE+MBD
565 meV/molecule
2.9 kcal/mol
due to screening
and many-body
VdW effects
Experiment
518-560 meV/molecule

Many-body vdW effects at play: Ellipticine
BLYP+DCACP
-37 kcal/mol
PBE+vdW
-46.6 kcal/mol
PBE+MBD
-55.0 kcal/mol
Lin, von Lilienfeld, Coutinho-Neto, Tavernelli, Rothlisberger, J. Phys.
Chem. B (2007); von Lilienfeld and Tkatchenko, J. Chem. Phys. (2010).
Many-body
vdW Energy
Overview
Introduction
Why do we care?
Motivation
First attempts
Applications
Outlook
BG/Q
(Mira)
Argonne Leadership Computing Facility promotes open science internationally

through INCITE program (http://www.alcf.anl.gov/)
Systems:
Large and crowded
Many
Methods: High quality (QMC, MBPT, CCSD(T) ...)
Acknowledgments
Rothlisberger, EPFL
Tkatchenko, FHI
Tavernelli, EPFL
DiStasio, Princeton
Sebastiani, FU Berlin
Dobson, Griffith U
This research used resources of the Argonne Leadership Computing Facility at

Argonne National Laboratory, which is supported by the Office of Science of the
U.S. Department of Energy under contract DE-AC02-06CH11357.
S22 database: Comparison with

other approaches
S22 CCSD(T): Jurecka, Sponer, Cerny, Hobza, PCCP (2006); Scherrill et al., JCP (2010).

The current state-of-the-art
(Grimme, Becke, Tkatchenko/Scheffler)
Effective screening and
two-body energy
The new state-of-the-art:

Full many-body screening
and energy for a system of
quantum oscillators
A
B
Valid for
small molecules or
homogeneous dielectrics
E
C
Valid for small and large

molecules, insulators, metals,
interfaces, ...

C6 coefficients: 1225 atomic/molecular dimers
TS-vdW
TS-vdW+SCS
A. Tkatchenko and M. Scheffler, PRL (2009)

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Dispersion Correcting Atom Centered

Potentials (DCACP) and Many-Body

O. Anatole von Lilienfeld

What's the problem with vdW?

Atom-Electron approach (DCACP)

Atom-Atom approach (MBD)

Many-body dispersion in DFT

3-body dispersion effects

Many-body dispersion effects

``There is plenty of room at the bottom'' (Feynman)

Adhesion, adsorption, physisorption

Liquid phase (Solid covalent, Gas ideal)

Nano- and meso-scale objects

Papers by D. Andrienko et al,

Why do we care? compound design

A Franceschetti & A Zunger, Nature (1999)

What's the problem with vdW?

What's the problem with vdW?

SAPT-DFT: Explicit energy expansion for weakly interacting moieties

Empirical density functionals (Truhlar et al. JCP (2006), Goddard

Empirical atom centered potentials (von Lilienfeld, Tavernelli,

Interatomic (pairwise or beyond) dispersion corrections

What's the problem with vdW?

Dion, Rydberg, Schroeder, Langreth, Lundqvist, PRL (2004).

What's the problem with vdW?

Local corr.: LDA

Local corr.: LDA

(*) Vydrov and van Voorhis, PRA (2010).

What's the problem with vdW?

Atom-Electron approach (DCACP)

Atom-Atom approach (MBD)

Many-body dispersion in DFT

3-body dispersion effects

Many-body dispersion effects

Dispersion corrected atom

Feynman, Phys Rev (1939)

Feynman, Phys Rev (1939)

Feynman, Phys Rev (1939)

Feynman, Phys Rev (1939)

Add atom centered potential to external potential in SCF

Act weakly on electrons in outer low density regions

Atom-electron corrections not unusual in solid state

relativistic effects for heavy atoms

dispersion corrected atom centered potentials

self-interaction correction (Pollmann (2006))

band-gap correction (van de Walle (2007))

What's the problem with vdW?

Atom-Electron approach (DCACP)

Atom-Atom approach (MBD)

Many-body dispersion in DFT

3-body dispersion effects

Many-body dispersion effects

von Lilienfeld, Tavernelli, Sebastiani, Roethlisberger, PRL (2004)

von Lilienfeld, Tavernelli, Sebastiani, Roethlisberger, PRL (2004);

Tapavizca, Lin, von Lilienfeld, Tavernelli, Coutinho-Neto, Roethlisberger, JCTC (2007)

Lin, von Lilienfeld, Coutinho-Neto, Tavernelli, Roethlisberger, JCPA (2007)

Roethlisberger group: http://lcbcpc21.epfl.ch/DCACP/DCACP.html

Tavernelli et al, Phys Rev B (2009)

What's the problem with vdW?

Atom-Electron approach (DCACP)

Atom-Atom approach (MBD)

Many-body dispersion in DFT

3-body dispersion effects

Many-body dispersion effects