Extensions to GPAW:from polarizable environments to excited state properties

A. Held, R. v. Waldenfels, O. Brügner, M.Hassan, M. Walter

22.5.2013 Michael Walter 2

Outline

* effective vdW scheme graphene – benzene interaction

* excited state forces vibrational resolved spectra

* PCM model

22.5.2013 Michael Walter 3

Distinct approaches to missing vdW

E xc [n ]=E xGGA [n ]+E c

nl[n]

E cnl [n ]=

12∫d

3r∫d 3 r ' n ( r )Φ (r , r ' )n (r ' )

vdW-DF: nonlocal exchange-kernel

(semi) empirical correction GGA energy (DFT-D)

E [n ]=E xcGGA [n ]+

12 ∑A , B

f (RAB)C 6, AB

RAB6

22.5.2013 Michael Walter 5

TS09 non-empirical C6

E [n ]=E xcGGA [n ]+

12 ∑a ,b

f (RAB)C6AB

RAB6

Heteronuclear related to homonuclear terms

Environment influences coefficients

C6ABeff

=( V Aeff

V Afree )

2

C6ABfree

22.5.2013 Michael Walter 6

Application to the S26 test set

=> very good energetics for small molecules

22.5.2013 Michael Walter 7

Polymer – graphene(oxide) interaction

Polystyrol

22.5.2013 Michael Walter 8

Van der Waals Polymer-GO

G1B1

H3

22.5.2013 Michael Walter 11

Donor-acceptor complexes

22.5.2013 Michael Walter 12

PTCDA

HOMO LUMO

22.5.2013 Michael Walter 13

Excited state forces (numeric)

22.5.2013 Michael Walter 14

Excellent comparison to experiment

22.5.2013 Michael Walter 15

Polarizable contiuum (PCM)

22.5.2013 Michael Walter 16

Evaluation of the terms

Poisson eqtn in presence of a dielectric medium ε(r)

Cavity

ΔGcav=γ A A=A({RavdW })

Pauli-repulsion

G int∝∫d rρ(r)g (r)

22.5.2013 Michael Walter 17

Charged Systems

22.5.2013 Michael Walter 18

Charged Systems ε ≠1

22.5.2013 Michael Walter 19

Fitting test set 13 molecules

22.5.2013 Michael Walter 20

Larger range of molecules

22.5.2013 Michael Walter 21

accurate forces

22.5.2013 Michael Walter 22

Gold clusters in ionic liquids

Experiment Simulation

Mertens et al Angew. Chem. (2011)

C[z] = e2 / (E[z-1]-2E[z]+E[z+1])

22.5.2013 Michael Walter 23

Gold clusters in ionic liquids

Experiment Simulation

Mertens et al Angew. Chem. (2011)

22.5.2013 Michael Walter 24

Thanks to

GroupMichael MoselerRolf WürdemannAlexander HeldMohamed HassanMathias ListRut v. Waldenfels

GPAW contributors

Computational resourcesRZ JülichBWgrid Freiburg

22.5.2013 Michael Walter 25

Reibung (Tribologie)

Reibung und Verschleiß: ~ 5% Bruttoszialprodukt

~120 Mrd €/Jahr in Deutschland

22.5.2013 Michael Walter 26

Katalyse

Metallpartikel Pd,Rh,Pt

CO, NOx, CxHy

22.5.2013 Michael Walter 27

TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2 CO + O2 → 2 CO

2

22.5.2013 Michael Walter 28

TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

2 CO + O2 → 2 CO

2

22.5.2013 Michael Walter 29

TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

3. Zugabe von CO

2 CO + O2 → 2 CO

2

22.5.2013 Michael Walter 30

Katalytisches Palladium

22.5.2013 Michael Walter 31

Katalytisches Palladium

22.5.2013 Michael Walter 32

Organische Solarzellen

ℏω+D+A → D*+A → D++A-

Donor

Akzeptor

22.5.2013 Michael Walter 33

Molekulare Fingerabdrücke

Experiment (Wewer 2004)

Simulation (R. v. Waldenfels 2012)

Floureszenz- Spektroskopie von PTCDA

22.5.2013 Michael Walter 34

TPD Experimente (TU München)

2 CO + O2 → 2 CO

2