Application of Density Functional Theory to Scanning

Tunneling Microscopy

Noel O’BoyleHan 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

Ene

rgy

(eV

)

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