Extensions to GPAW

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Extensions to GPAW

Extensions to GPAW:

from polarizable environments to

excited state properties

A. Held, R. v. Waldenfels, O. Brügner,

M.Hassan, M. Walter


Outline

* effective vdW scheme

graphene – benzene interaction

* excited state forces

vibrational resolved spectra

* PCM model

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Distinct approaches to missing vdW

vdW-DF: nonlocal exchange-kernel

E xc [n ]=E x

GGA

[n ]+E c nl [n]

E c

nl

[n]= 1 2 ∫ d 3 r∫ d 3 r ' n (r)Φ (r , r ' ) n (r ' )

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

GGA

E [n ]=E xc [n ]+ 1 2 ∑ f (R A , B AB) C 6, AB

6

R AB

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TS09 non-empirical C 6

GGA

E [n ]=E xc [n ]+ 1 2 ∑ a ,b

f (R AB) C 6AB

6

R AB

Heteronuclear related to homonuclear terms

Environment influences coefficients

eff

C 6AB

=( V eff )2

A free

C

free 6AB

V A

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Application to the S26 test set

=> very good energetics for small molecules

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Polymer – graphene(oxide) interaction

Polystyrol

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Van der Waals Polymer-GO

H3

B1

G1

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Donor-acceptor complexes

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PTCDA

HOMO

LUMO

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Excited state forces (numeric)

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Excellent comparison to experiment

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Polarizable contiuum (PCM)

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Evaluation of the terms

Cavity

Δ G cav

=γ A A=A({ R a vdW })

Pauli-repulsion

G int ∝∫ d r ρ(r) g (r)

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

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Charged Systems

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Charged Systems ε ≠1

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Fitting test set 13 molecules

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Larger range of molecules

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accurate forces

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Gold clusters in ionic liquids

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

Experiment

Simulation

Mertens et al Angew. Chem. (2011)

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Gold clusters in ionic liquids

Experiment

Simulation

Mertens et al Angew. Chem. (2011)

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Thanks to

Group

Michael Moseler

Rolf Würdemann

Alexander Held

Mohamed Hassan

Mathias List

Rut v. Waldenfels

GPAW contributors

Computational resources

RZ Jülich

BWgrid Freiburg

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Reibung (Tribologie)

Reibung und Verschleiß: ~ 5% Bruttoszialprodukt

~120 Mrd €/Jahr in Deutschland

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Katalyse

CO, NOx, CxHy

Metallpartikel Pd,Rh,Pt

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TPD Experimente (TU München)

2 CO + O 2

→ 2 CO 2

1. Cluster Deposition (90 K)

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TPD Experimente (TU München)

2 CO + O 2

→ 2 CO 2

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

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TPD Experimente (TU München)

2 CO + O 2

→ 2 CO 2

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

3. Zugabe von CO

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Katalytisches Palladium

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Katalytisches Palladium

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Organische Solarzellen

ħ ω+D+A → D * +A → D + +A -

Donor

Akzeptor

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Molekulare Fingerabdrücke

Experiment (Wewer 2004)

Simulation (R. v. Waldenfels 2012)

Floureszenz- Spektroskopie

von PTCDA

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TPD Experimente (TU München)

2 CO + O 2

→ 2 CO 2

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