application of density functional theory to scanning tunneling microscopy

Application of Density Functional Theory to Scanning

Tunneling Microscopy

Noel O’Boyle

Han Vos

Dublin City University

National Centre for Sensor Research

Gold Surface

STM tip

Osmium (II/III) complex

Cou

nter

Ref

eren

ceBias voltage

In situ Scanning TunnelingMicroscopy

Os

Cl N

N

N

N N

N

+

II

N

Os

Cl N

N

N N

N

+

II

[Os(bpy)2(P0P)Cl]+ [Os(bpy)2(P2P)Cl]+

[Os(bpy)2(P0P)Cl]+ [Os(bpy)2(P2P)Cl]+

DFT (B3LYP/LanL2DZ)

[O s I I(b p y ) 2 (P 0 P )C l] + [O s I I(b p y ) 2 (P 2 P )C l] +

L U M O L U M O

H O M O H O M O

[O s I I I(b p y ) 2 (P 0 P )C l] 2 + [O s I I I(b p y ) 2 (P 2 P )C l] 2 +

L U M O L U M O

H O M O H O M O

0.0 0.2 0.4 0.6 0.8 1.0

-9

-8

-7

-6

-5

-4

-3

0.0 0.2 0.4 0.6 0.8 1.0-10

-9

-8

-7

-6

-5

-4

-3

P2PP0P

Ene

rgy

(eV

)

Os P0P/P2P Cl bpy

HOMO HOMO

LUMO LUMO

[Os(bpy)2(P0P)Cl]+ [Os(bpy)2(P2P)Cl]+

0.0 0.2 0.4 0.6 0.8 1.0

-13

-12

-11

-10

-9

-8

-7

0.0 0.2 0.4 0.6 0.8 1.0-10

-9

-8

-7

-6

-5

-4

-3

OsIIIOsII

Ene

rgy

(eV

)

Os P0P Cl bpy

HOMO HOMO

LUMO

LUMO

-11

-10

-9

-8

-7

-6

-5

-4

-3

-2

Au Os

-10

-9

-8

-7

-6

-5

-4

-3

-2

En

erg

y (e

V)

Au

-10

-9

-8

-7

-6

-5

-4

-3

-2

Os

HOMO HOMO

HOMO

LUMO LUMO LUMO

Acknowledgements:SUSANA network Prof. Jens UlstrupProf. Han Vos Dr. Tim Albrecht