Dispersion Correcting Atom Centered Potentials (DCACP) and Many ... - Delaware Physics ·...

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

Dispersion (MBD) contributions to interatomic vdW forces

O. Anatole von LilienfeldCurrent: 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)

Supra-molecular systems, liquids, and solids

Ionic systems

Metals, alloys, Semi-conductors, defects

Hybrid organic/inorganicinterfaces

Low-dimensional systemsWhy do we care?

Physico-chemical Properties and reactions

6A Franceschetti & A Zunger, Nature (1999)

Science (1991)

Many more– Norskov et al (Stanford/DTU)– Curtarolo&Beratan&Yang (Duke)– Ceder (MIT)– Wolverton (Northwestern)– Zunger (NREL)– Yamashita (UT)– von Lilienfeld (ANL)

Why do we care? – compound design

Ar Ar

What's the problem with vdW?

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 ...

➢ 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


Dion, Rydberg, Schroeder, Langreth, Lundqvist, PRL (2004).Lee, Murray, Kong, Lundqvist, Langreth, PRB (2010).


Langreth-Lundqvist functional

Langreth-Lundqvist functional (vdW-DF-04 and vdW-DF-10)

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

vdW-DF-04

Exchange: revPBE

Local corr.: LDA

No free parameters

C6 error: ~ 20%

vdW-DF-10

Exchange: PW86

Local corr.: LDA

2 parameters

C6 error: ~ 60%(*)


Overview

➔ Introduction






Dispersion corrected atom centered potentials (DCACP)

General idea – electron-electron– atom-atom→atom-electron

Motivation

Feynman, Phys Rev (1939)


Motivation

R


Motivation

R

R 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






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)

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

DCACP applications

DCACP applications

Tavernelli et al, Phys Rev B (2009)

Overview

➔ Introduction






Many-body dispersion in DFT

A BRAB

Pair-wise corrected DFT

Tkatchenko & von Lilienfeld, PRB (2008)

CoulombScreening

Many-bodyvdW Energy

A BRAB

r1

r2


Many-bodyvdW Energy


Many-bodyvdW Energy



For rare gas crystals, experimentalMBC estimated to be up to 10% of cohesive energy

Functional MBC

LDA 35 %

PBE 50 %

TPSS 80 %

Overview

➔ Introduction






Many-bodyvdW Energy

3-body dispersion effects

von Lilienfeld & Tkatchenko, JCP (2010)


von Lilienfeld & Tkatchenko, JCP (2010) Tkatchenko&Scheffler, PRL (2009)

Many-bodyvdW Energy




von Lilienfeld & Tkatchenko, JCP (2010) Tkatchenko&Scheffler, PRL (2009)

Damping according to Tang&Toennis

Many-bodyvdW Energy



Overview

➔ Introduction






Many-bodyvdW Energy

Many-body dispersion effects

Tkatchenko, von Lilienfeld, DiStasio, accepted in PNAS (2012)

CoulombScreening

Many-bodyvdW Energy

A BRAB

r1

r2

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

C6⊥ C6∥ C6iso

TS-vdW: 166 161 165 +SCS: 89 692 223 LR-CCSD: 115 638 238 (Reference)

All values in HartreeBohr6


C6 coefficients: from small to large silicon clusters

TDLDA: S. Botti et al., PRB (2008)

27% error


PBE(0)+MBD: S22 database

MAREPBE+vdW 9.1%PBE+MBD 5.4%PBE0+MBD 4.2%

PBE+vdWPBE+MBD

PBE0+MBD

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

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)

Important features of DFT+MBD

A

CD

F E

B



Many-bodyvdW Energy



Many-body vdW effects at play: Benzene molecular crystal

PBE+vdW690 meV/molecule

PBE+MBD565 meV/molecule

Experiment518-560 meV/molecule

2.9 kcal/moldue to screeningand many-bodyVdW effects



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 effects at play: Ellipticine


Many-bodyvdW Energy



Overview

➔ Introduction






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 Tavernelli, EPFL Sebastiani, FU Berlin

Tkatchenko, FHI DiStasio, PrincetonDobson, 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

A

B

The new state-of-the-art:Full many-body screening and energy for a system of

quantum oscillators

A

CD

F E

B

Valid for small molecules or

homogeneous dielectrics

Valid for small and large molecules, insulators, metals,

interfaces, ...


C6 coefficients: 1225 atomic/molecular dimers

A. Tkatchenko and M. Scheffler, PRL (2009)

TS-vdWTS-vdW+SCS


Dispersion Correcting Atom Centered Potentials (DCACP) and Many ... - Delaware Physics ·...

Documents

Transcript of Dispersion Correcting Atom Centered Potentials (DCACP) and Many ... - Delaware Physics ·...