extensions to gpaw: from polarizable environments to excited state properties · 2013. 5. 23. ·...

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

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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

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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

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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

G1B1

H3

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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

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)

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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

Experiment Simulation

Mertens et al Angew. Chem. (2011)

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

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Gold clusters in ionic liquids

Experiment Simulation

Mertens et al Angew. Chem. (2011)

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Thanks to

GroupMichael MoselerRolf WürdemannAlexander HeldMohamed HassanMathias ListRut v. Waldenfels

GPAW contributors

Computational resourcesRZ JülichBWgrid Freiburg

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Reibung (Tribologie)

Reibung und Verschleiß: ~ 5% Bruttoszialprodukt

~120 Mrd €/Jahr in Deutschland

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Katalyse

Metallpartikel Pd,Rh,Pt

CO, NOx, CxHy

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TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2 CO + O2 → 2 CO

2

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TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

2 CO + O2 → 2 CO

2

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TPD Experimente (TU München)

1. Cluster Deposition (90 K)

2. Sauerstoffzugabe

3. Zugabe von CO

2 CO + O2 → 2 CO

2

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Katalytisches Palladium

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Katalytisches Palladium

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Organische Solarzellen

ℏω+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 + O2 → 2 CO

2