«Su

rfac

es»

http

://ac

tu.u

niv-

fcom

te.fr

/site

s/de

faul

t/file

s/m

olec

ules

.jpg

Ann

e La

foss

eO

rsay

Inst

itute

for M

olec

ular

Sci

ence

sU

nive

rsité

Par

is-S

ud, U

nive

rsité

Par

is-S

acla

y

«Su

rfac

es»

Con

text

: m

olec

ules

& m

olec

ular

pro

cess

es a

t sol

idsu

rface

s&

pro

be b

y vi

brat

iona

l spe

ctro

scop

y(‡

HR

EE

LS H

igh

Res

olut

ion

Ele

ctro

n E

nerg

y Lo

ss S

pect

rosc

opy)

Het

erog

eneo

us c

atal

ysis

–El

emen

tary

ste

ps

H. O

ver,

Y.D

.Kim

, A. P

. Sei

tson

en, S

. Wen

dt, E

. Lun

dgre

n, M

. Sch

mid

, P. V

arga

, A. M

orga

nte,

G. E

rtl, Sci

ence

287(

5457

):147

4-14

76(2

000)

.Ato

mic

-Sca

le S

truct

ure

and

Cat

alyt

ic R

eact

ivity

of t

he R

uO2(

110)

Sur

face

.

O layer

Ru

Obr

idge

Che

mic

al P

roce

sses

Hab

er-B

osch

N2

+ 3

H2‡

2 N

H3

Fisc

her-

Trop

sch

H2

+ C

O ‡

met

hano

l, liq

uid

fuel

s«

Thre

eway

» ca

taly

tic c

onve

rter

N

Ox,

CO

& H

C ‡

H2O

+C

O2

+N2

G. E

rtl –

Fritz

-Hab

er-In

stitu

t der

Max

-Pla

nck-

Ges

ells

chaf

t (B

erlin

)20

07 :

Che

mis

try N

obel

Pric

e

RuO

2(11

0)A

dsor

ptio

n / D

esor

ptio

nC

hem

isor

ptio

nD

ecom

posi

tion

/Rea

ctiv

ityS

urfa

ce /

Site

s

Sens

ors

–M

olec

ular

pla

tform

sA

im is

to c

ombi

ne th

e pr

oper

ties

of th

e bu

lk m

ater

ial t

o th

e su

rface

pr

oper

ties

that

are

cho

sen

and

adap

ted

acco

rdin

g to

spe

cific

app

licat

ions

Che

mic

al fu

nctio

naliz

atio

n: c

hang

ing

the

surfa

ce te

rmin

atio

ns‡

Tuni

ng o

f the

mec

hani

cal,

elec

troni

cal,

chem

ical

pro

perti

esof

the

surfa

ce, w

ith s

patia

l res

olut

ion

whe

n re

quire

d

F. S

chre

iber

, J. P

hys.

: Con

dens

. Mat

ter 1

6 (2

004)

R88

1. S

elf-a

ssem

bled

mon

olay

ers:

from

‘sim

ple’

mod

el

syst

ems

tobi

ofun

ctio

naliz

edin

terfa

ces

Ads

orpt

ion

Che

mis

orpt

ion

/ Phy

siso

rptio

nS

patia

l arr

ange

men

ts?

«Su

rfac

es»

Con

text

: m

olec

ules

& m

olec

ular

pro

cess

es a

t sol

idsu

rface

s&

pro

be b

y vi

brat

iona

l spe

ctro

scop

y(‡

HR

EE

LS H

igh

Res

olut

ion

Ele

ctro

n E

nerg

y Lo

ss S

pect

rosc

opy)

Ads

orpt

ion

/ Des

orpt

ion

/ Diff

usio

nC

hem

isor

ptio

n / P

hysi

sorp

tion

Dec

ompo

sitio

n / R

eact

ivity

Sur

face

/ D

efec

ts /

Site

sP

erio

dic

arra

ngem

ents

/ O

rient

atio

n

Con

tent

sI

Sur

face

s? In

terfa

ces?

Sub

stra

tes

How

doe

s a

solid

sur

face

look

s lik

e: a

tom

ic d

ensi

ties

& d

efec

ts?

Sur

face

orie

ntat

ions

–M

onoc

ryst

allin

e ph

ases

Rel

axat

ions

-re

cons

truct

ions

II M

olec

ular

ads

orpt

ion

Sin

gle

mol

ecul

e ad

sorp

tion

Phy

siso

rptio

n / C

hem

isor

ptio

nO

rient

atio

n &

ads

orpt

ion

site

Sup

porte

d m

olec

ular

ass

embl

ies

Mol

ecul

e/su

bstra

te v

s. in

term

olec

ular

inte

ract

ions

Ord

ered

mol

ecul

ar p

hase

s: 2

exa

mpl

es o

f sel

f-as

sem

bled

mol

ecul

ar la

yers

III P

robi

ng m

olec

ular

reac

tivity

at s

urfa

ces

usin

g vi

brat

iona

l spe

ctro

scop

yV

ibra

tiona

l mod

es &

vib

ratio

nal s

pect

rosc

opy

tech

niqu

es

V

ibra

tiona

l mod

es o

f an

«ad

sorb

ate-

subs

trate

» sy

stem

Sur

face

vib

ratio

nal s

pect

rosc

opy

tech

niqu

esE

lect

ron

ener

gy lo

ss s

pect

rosc

opy

(HR

EE

LS) –

Prin

cipl

e &

spe

ctro

met

erIn

tram

olec

ular

reac

tion

-The

rmal

ly in

duce

d is

omer

izat

ion

of m

olec

ular

sw

itche

sP

roce

sses

in h

eter

ogen

eous

cat

alys

is fo

llow

ed s

tep

by s

tep

http

://w

ww

.ccn

.yam

anas

hi.a

c.jp

/~ko

mila

b/ke

nkyu

-e.h

tml

TiO

2(1

10)–

Ato

mic

arr

ange

men

ts

Ato

mic

sur

face

den

sity

m(Fe

) = 7

,874

g/c

m3

M(F

e) =

55,

845

g.m

ol-1

1,9.

1015

atom

es.c

m-2

Mod

el fo

r a re

alis

tic s

urfa

ce -

mod

el T

erra

ce-S

tep-

Kin

k (T

SK)

Line

ar /

loca

lized

def

ects

Terr

ace

Rou

gh s

urfa

ce: 1

0-20

% a

tom

s be

long

to s

teps

an

d 5%

to k

inks

r dis

loc~

106 -

108

cm-2

met

als

& io

nic

crys

tals

r dis

loc~

104 -

106

cm-2

sem

i-con

duct

ors

& in

sula

tors

0,01

ML

of a

dato

ms

«sc

rew

» di

sloc

atio

n

«ed

ge»

disl

ocat

ion

step

kink

Impu

rity

adat

om

step

ada

tom

terr

ace

adat

om

step

vac

ancy

terr

ace

vaca

ncy

Surf

ace

orie

ntat

ions

-M

iller

inde

xes

(h k

l)

1

2

3

(1/l)

(1/h

)(1

/k)

(h k

l) =

(6 2

3)

Cut

thro

ugh

the

bulk

mat

eria

l par

alle

l to

sele

cted

pla

nes

Low

-inde

xes

mon

ocry

stal

line

phas

esEx

ampl

e: fa

ce-c

ente

red

cubi

c (F

CC

) cry

stal

s

Mat

eria

ls :

Au,

Pt,

Pd,

Ni,

Cu,

Al

Sur

face

com

paci

ty Ø

Hig

h in

dexe

s m

onoc

ryst

allin

e ph

ases

-Te

rrac

esE

xam

ple:

Pt(7

55)

Pt [

7(11

1)x(

100)

]

Surf

ace

rela

xatio

ns &

reco

nstr

uctio

ns

norm

alpa

ralle

l

Rel

axat

ion

Al(1

10) (

FCC

) –N

orm

al re

laxa

tion

(I-V

LE

ED

, And

erse

n J.

Phy

s. C

198

4)

D12

=-8

,6 %

D23

= +5

,0 %

D34

=-1

,6 %

Dan

glin

g bo

nds ‡

Sur

face

dim

ers

H.H

. Far

rell

et a

l., P

RB

30

(198

4)

Mor

edr

astic

rela

xatio

ns-S

i(100

) (2×

1) re

cons

truc

tion

http

://w

ww

.fhi-b

erlin

.mpg

.de/

th/p

erso

nal/h

erm

ann/

Si1

00un

.gif

Si(1

11)-(

7x7)

Dim

erA

dato

mSt

acki

ng fa

ult (

DA

S)

http

://w

ww

.fhi-b

erlin

.mpg

.de/

th/p

erso

nal/

herm

ann/

Si1

00un

.gif

Taka

ynag

i et a

l. 19

85ht

tp://

std2

.fic.

uni.l

odz.

pl/~

pkow

a/st

mga

llery

.htm

l

Au(

111)

-(22×

√3)

Her

ringb

one

reco

nstr

uctio

n

Con

tent

sI

Sur

face

s? In

terfa

ces?

Sub

stra

tes

How

doe

s a

solid

sur

face

look

s lik

e: a

tom

ic d

ensi

ties

& d

efec

ts?

Sur

face

orie

ntat

ions

–M

onoc

ryst

allin

e ph

ases

Rel

axat

ions

-re

cons

truct

ions

II M

olec

ular

ads

orpt

ion

Sin

gle

mol

ecul

e ad

sorp

tion

Phy

siso

rptio

n / C

hem

isor

ptio

nO

rient

atio

n &

ads

orpt

ion

site

Sup

porte

d m

olec

ular

ass

embl

ies

Mol

ecul

e/su

bstra

te v

s. in

term

olec

ular

inte

ract

ions

Ord

ered

mol

ecul

ar p

hase

s: 2

exa

mpl

es o

f sel

f-as

sem

bled

mol

ecul

ar la

yers

III P

robi

ng m

olec

ular

reac

tivity

at s

urfa

ces

usin

g vi

brat

iona

l spe

ctro

scop

yV

ibra

tiona

l mod

es &

vib

ratio

nal s

pect

rosc

opy

tech

niqu

es

V

ibra

tiona

l mod

es o

f an

«ad

sorb

ate-

subs

trate

» sy

stem

Sur

face

vib

ratio

nal s

pect

rosc

opy

tech

niqu

esE

lect

ron

ener

gy lo

ss s

pect

rosc

opy

(HR

EE

LS) –

Prin

cipl

e &

spe

ctro

met

erIn

tram

olec

ular

reac

tion

-The

rmal

ly in

duce

d is

omer

izat

ion

of m

olec

ular

sw

itche

sP

roce

sses

in h

eter

ogen

eous

cat

alys

is fo

llow

ed s

tep

by s

tep

Phys

isor

ptio

n &

Che

mis

orpt

ion

–M

ain

feat

ures

1D m

odel

for t

he a

dsor

bate

-sub

stra

te in

tera

ctio

n en

ergy d

(M -

subs

trate

)

0

Phys

isor

ptio

n &

Che

mis

orpt

ion

–M

ain

feat

ures

Sub

stra

te: s

light

dep

ende

nce

upon

its

com

posi

tion,

virt

ually

inde

pend

ent o

f sur

face

atom

ic g

eom

etry

, no

sign

ifica

nt e

lect

roni

c de

nsity

redi

strib

utio

nA

dsor

bate

: rel

ated

to fa

ctor

s lik

e m

olec

ular

mas

s an

d po

larit

yno

sig

nific

ant e

lect

roni

c de

nsity

redi

strib

utio

nN

on d

isso

ciat

ive

& R

ever

sibl

e

1D m

odel

for t

he a

dsor

bate

-sub

stra

te in

tera

ctio

n en

ergy d

(M -

subs

trate

)

Wea

k in

tera

ctio

n en

ergy

0.05

-0.4

eV

(5-4

0 kJ

mol

-1)

(Van

der

Waa

ls, p

-sta

ckin

g)

at la

rge

dist

ance

Phys

isor

ptio

n &

Chi

mis

orpt

ion

–M

ain

feat

ures

Sub

stra

te: s

ubst

antia

l var

iatio

n be

twee

n m

ater

ials

, mar

ked

varia

tion

betw

een

crys

tal

plan

es &

sur

face

reco

nstru

ctio

n, s

igni

fican

t ele

ctro

nic

dens

ity re

dist

ribut

ion

Ads

orba

te: s

igni

fican

t ele

ctro

nic

dens

ity re

dist

ribut

ion

Ofte

n di

ssoc

iativ

e &

may

be

irrev

ersi

ble

1D m

odel

for t

he a

dsor

bate

-sub

stra

te in

tera

ctio

n en

ergy d

(M -

subs

trate

)

Stro

ng in

tera

ctio

n en

ergy

0.

4-8.

3 eV

(40

-800

kJ

mol

-1)

(cov

alen

t / io

nic

chem

ical

bo

nd)

at s

hort

dist

ance

Sing

le m

olec

ule

adso

rptio

n -O

rient

atio

n &

ads

orpt

ion

site

H2

/ W(1

00)

Den

sity

Fun

ctio

nal T

heor

y us

ing

a pl

ane-

wav

e, p

seud

opot

entia

l met

hod

and

grad

ient

-cor

rect

ed e

xcha

nge

corr

elat

ion

ener

gies

Pot

entia

lene

rgy

surfa

ce (P

ES

) E

(r,q

,f,X

,Y,Z

)

WW

WW

M. K

ay, M

. Kay

, G. R

. Dar

ling,

S. H

ollo

way

, J. C

hem

. Phy

s. 1

08 (1

998)

461

4. C

ompa

ring

quan

tum

and

cla

ssic

al d

ynam

ics:

H2

diss

ocia

tion

on W

(100

) fi2D

con

tour

map

s(r,

Z)

M. K

ay, M

. Kay

, G. R

. Dar

ling,

S. H

ollo

way

, J. C

hem

. Phy

s. 1

08 (1

998)

461

4Phy

siso

rptio

n

Sing

le m

olec

ule

adso

rptio

n -O

rient

atio

n &

ads

orpt

ion

site

H2

/ W(1

00)

Act

ivat

ed

diss

ocia

tive

chem

isor

ptio

n

Dire

ctdi

ssoc

iativ

ech

emis

orpt

ion

Sing

le m

olec

ule

adso

rptio

n -O

rient

atio

n &

ads

orpt

ion

site

H2

/ W(1

00)

M. K

ay, M

. Kay

, G. R

. Dar

ling,

S. H

ollo

way

, J. C

hem

. Phy

s. 1

08 (1

998)

461

4

Site

dep

ende

nt, 1

D p

oten

tials

as

a fu

nctio

n of

the

reac

tion p

ath

Con

tent

sI

Sur

face

s? In

terfa

ces?

Sub

stra

tes

How

doe

s a

solid

sur

face

look

s lik

e: a

tom

ic d

ensi

ties

& d

efec

ts?

Sur

face

orie

ntat

ions

–M

onoc

ryst

allin

e ph

ases

Rel

axat

ions

-re

cons

truct

ions

II M

olec

ular

ads

orpt

ion

Sin

gle

mol

ecul

e ad

sorp

tion

Phy

siso

rptio

n / C

hem

isor

ptio

nO

rient

atio

n &

ads

orpt

ion

site

Sup

porte

d m

olec

ular

ass

embl

ies

Mol

ecul

e/su

bstra

te v

s. in

term

olec

ular

inte

ract

ions

Ord

ered

mol

ecul

ar p

hase

s: 2

exa

mpl

es o

f sel

f-as

sem

bled

mol

ecul

ar la

yers

III P

robi

ng m

olec

ular

reac

tivity

at s

urfa

ces

usin

g vi

brat

iona

l spe

ctro

scop

yV

ibra

tiona

l mod

es &

vib

ratio

nal s

pect

rosc

opy

tech

niqu

es

V

ibra

tiona

l mod

es o

f an

«ad

sorb

ate-

subs

trate

» sy

stem

Sur

face

vib

ratio

nal s

pect

rosc

opy

tech

niqu

esE

lect

ron

ener

gy lo

ss s

pect

rosc

opy

(HR

EE

LS) –

Prin

cipl

e &

spe

ctro

met

erIn

tram

olec

ular

reac

tion

-The

rmal

ly in

duce

d is

omer

izat

ion

of m

olec

ular

sw

itche

sP

roce

sses

in h

eter

ogen

eous

cat

alys

is fo

llow

ed s

tep

by s

tep

Ver

y lo

w c

over

age

–M

obile

ads

orba

tes

Form

atio

n of

«st

riped

» do

mai

ns

Sat

urat

ion

of th

e ly

ing

dow

n ph

ase

Pha

se tr

ansi

tion

tow

ards

the

stan

ding

phas

e

SA

M o

f sta

ndin

g m

olec

ules

com

plet

ed

Supp

orte

d de

nse

crys

talli

ne m

olec

ular

film

sSc

enar

io fo

r SA

M fo

rmat

ion

& in

volv

edin

tera

ctio

ns

Stro

ngm

olec

ule/

subs

trate

inte

ract

ion:

E ads

≈E l

≈1,

7-4,

6eV

(cov

alen

tbon

d)In

term

olec

ular

inte

ract

ions

:Ein

t≈

0,7

eV (V

an d

er W

aals

,p-s

tack

ing)

Con

text

: For

mat

ion

of a

Sel

f-Ass

embl

ed M

onol

ayer

s (S

AM

s), w

hich

can

be

used

as

mol

ecul

ar p

latfo

rms

for s

enso

r dev

elop

men

t

Supp

orte

d de

nse

crys

talli

ne m

olec

ular

fil

m

G.E

. Poi

rier,

Che

m. R

ev. 9

7 (1

997)

11

17. C

hara

cter

izat

ion

of O

rgan

osul

fur

Mol

ecul

ar M

onol

ayer

s on

Au(

111)

usi

ng

Sca

nnin

g Tu

nnel

ing

Mic

rosc

opy.

Mer

capt

ohex

anol

/ A

u(11

1)H

S-C

6H12

-OH

Rac

hel K

. Sm

ith, P

enel

ope

A. L

ewis

, Pau

l S. W

eiss

, Pro

g. S

urf.

Sci

. 75

(200

4) 1

. P

atte

rnin

g se

lf-as

sem

bled

mon

olay

ers.

250

Å×

250

Å

Supp

orte

d de

nse

crys

talli

ne m

olec

ular

film

sn-

deca

neth

iola

te- S

-(CH

2) 9-C

H3

/ Au(

111)

Com

pact

hex

agon

al

arra

ngem

ent o

f ad

sorb

ates

med

iate

d by

th

e un

derly

ing

subs

trat

eco

nditi

ons t

unne

l: V

écha

ntill

on=

-1V,

i tunn

el=

10pA

~5,

0Å

4.10

14m

olec

ules

.cm

-2

Mol

ecul

e/su

bstr

ate

vs. i

nter

mol

ecul

ar in

tera

ctio

nsN

i por

phyr

in d

imer

s on

the

Ag(

111)

sur

face

S.A

. Kra

snik

ov, N

.N. S

erge

eva,

Y.N

. Ser

geev

a, M

.O. S

enge

, A.A

. Caf

oll,

Phy

s. C

hem

. Che

m.

Phy

s., 2

010,

12,

666

6. S

elf-a

ssem

bled

row

s of

Ni p

orph

yrin

dim

ers

on th

e A

g(11

1) s

urfa

ce.

Con

text

for t

he s

tudy

of s

uppo

rted

porp

hyrin

s an

d po

rphy

rin o

ligom

ers:

Por

phyr

ins

are

capa

ble

of b

indi

ng &

re

leas

ing

gase

s‡

Che

mic

al &

gas

sen

sors

Por

phyr

ins

are

capa

ble

of a

ctin

g as

ac

tive

cent

er in

cat

alyt

ic re

actio

ns‡

Nan

opor

ous

cata

lytic

mat

eria

ls

(syn

thet

ic b

io-m

imet

ic d

evic

es)

~1,7

nm

~2,7 nm

Mol

ecul

e/su

bstr

ate

vs. i

nter

mol

ecul

ar in

tera

ctio

nsN

i por

phyr

in d

imer

s on

the

Ag(

111)

sur

face

S.A

.Kra

snik

ovet

al.,

Phy

s. C

hem

.Che

m. P

hys.

, 201

0, 1

2, 6

666.

~0,5

ML

clos

ed-p

acke

d is

land

s co

nsis

ting

of d

imer

row

s‡

Inte

rmol

ecul

ar b

ondi

ng is

stro

nger

then

the

mol

ecul

e/su

bstra

te in

tera

ctio

n as

exp

ecte

d fro

m a

low

reac

tivity

sub

stra

te

unoc

cupi

ed s

tate

s (V

sam

ple

= 1.

30V)

Mol

ecul

e/su

bstr

ate

vs. M

olec

ule/

mol

ecul

e in

tera

ctio

nsN

i por

phyr

in d

imer

s on

the

Ag(

111)

sur

face

S.A

.Kra

snik

ovet

al.,

Phy

s. C

hem

.Che

m. P

hys.

, 201

0, 1

2, 6

666.

Inte

rmol

ecul

ar

inte

ract

ion

thro

ugh

p-p

bond

ing

(effi

cien

t due

to th

e ph

enyl

ring

rota

tion)

Wea

km

olec

ule/

subs

trate

inte

ract

ion

: phy

siso

rptio

n th

roug

hm

olec

ular

p-e-

syst

emB

utst

rong

enou

ghto

alig

nth

edo

mai

nsal

ong

the

mai

n cr

ysta

llogr

aphi

cdi

rect

ions

of t

he

Ag(

111)

subs

trate

Con

tent

sI

Sur

face

s? In

terfa

ces?

Sub

stra

tes

How

doe

s a

solid

sur

face

look

s lik

e: a

tom

ic d

ensi

ties

& d

efec

ts?

Sur

face

orie

ntat

ions

–M

onoc

ryst

allin

e ph

ases

Rel

axat

ions

-re

cons

truct

ions

II M

olec

ular

ads

orpt

ion

Sin

gle

mol

ecul

e ad

sorp

tion

Phy

siso

rptio

n / C

hem

isor

ptio

nO

rient

atio

n &

ads

orpt

ion

site

Sup

porte

d m

olec

ular

ass

embl

ies

Mol

ecul

e/su

bstra

te v

s. in

term

olec

ular

inte

ract

ions

Ord

ered

mol

ecul

ar p

hase

s: 2

exa

mpl

es o

f sel

f-as

sem

bled

mol

ecul

ar la

yers

III P

robi

ng m

olec

ular

reac

tivity

at s

urfa

ces

usin

g vi

brat

iona

l spe

ctro

scop

yV

ibra

tiona

l mod

es &

vib

ratio

nal s

pect

rosc

opy

tech

niqu

es

V

ibra

tiona

l mod

es o

f an

«ad

sorb

ate-

subs

trate

» sy

stem

Sur

face

vib

ratio

nal s

pect

rosc

opy

tech

niqu

esE

lect

ron

ener

gy lo

ss s

pect

rosc

opy

(HR

EE

LS) –

Prin

cipl

e &

spe

ctro

met

erIn

tram

olec

ular

reac

tion

-The

rmal

ly in

duce

d is

omer

izat

ion

of m

olec

ular

sw

itche

sP

roce

sses

in h

eter

ogen

eous

cat

alys

is fo

llow

ed s

tep

by s

tep

Vibr

atio

nal m

odes

of a

n «

adso

rbat

e-su

bstr

ate

» sy

stem

Exa

mpl

e: C

O c

hem

isor

bed

on a

brid

ge s

ite o

f Ni(1

00) (

CFC

)

Inte

rnal

mol

ecul

ar m

odes

(3N-

5 / 3

N-6

)Fr

ustra

ted

trans

latio

ns (3

) and

rota

tions

(lib

ratio

ns) (

2/3)

Vibr

atio

nal s

pect

rosc

opy

tech

niqu

es to

pro

be m

olec

ular

sy

stem

s at

sur

face

s

HR

EELS

(Lec

ture

"Ele

ctro

n sc

atte

ring”

by

Šte

fan

Mat

ejčí

k)H

igh

Res

olut

ion

Ele

ctro

n E

nerg

y Lo

ss S

pect

rosc

opy

FTIR

(Lec

ture

“IR

and

far I

R s

pect

rosc

opy”

by

Knu

th A

smis

)•T

rans

mis

sion

•RA

IRS

, Ref

lect

ion-

Abs

orpt

ion

IR S

pect

rosc

opy

or IR

RA

S,

Infra

red

Ref

lect

ion

Abs

orpt

ion

•DR

or D

RIF

TS, D

iffus

e R

efle

ctan

ce IR

Fou

rier T

rans

form

Spe

ctro

scop

y•A

TR, A

ttenu

ated

Tot

al R

efle

ctan

ce &

MIR

, Mul

tiple

Inte

rnal

R

efle

ctio

n S

pect

rosc

opy

•PM

-IRR

AS

Pol

ariz

atio

n M

odul

atio

n In

frare

d R

efle

ctio

n-A

bsor

ptio

n S

pect

rosc

opy

SFG

-Sum

freq

uenc

y ge

nera

tion

spec

trosc

opy

STM

-IET

S–

Inel

astic

Ele

ctro

n Tu

nnel

ing

Spe

ctro

scop

y un

der a

n S

TM ti

p (d

2 I/dV

2sp

ectra

)

Elec

tron

ene

rgy

loss

spe

ctro

scop

y -P

rinci

ple

(In)e

last

ic s

catte

ring

of e

lect

rons

2 co

nser

vatio

n la

ws

•E

nerg

yE i

= E f

+ E l

oss

E los

s=

DE

= E

i–

Ef

: ene

rgy

loss

•M

omen

tum

p/ w

ave

vect

or k

(p=

ħk)

k i//

=k f

//+

q //+

G//

Dk//

=q /

/+G

//k

: wav

e ve

ctor

q: e

xcita

tion

wav

e ve

ctor

G: r

ecip

roca

l lat

tice

vect

or

HR

EEL

Spec

trom

eter

(Om

icro

n IB

500)

~ 40

cm

Ana

lyze

r

Mon

ochr

omat

or

Mai

n ex

cita

tion

mec

hani

sm -

Dip

olar

inte

ract

ion

with

the

dyna

mic

dipo

lem

omen

t

E th

e ex

citin

gel

ectri

cfie

ldat

the

inte

rfac

e

Exc

itatio

n pr

obab

ility

of a

vib

ratio

nal m

ode

Cha

rge

imag

e ef

fect

for

cond

uctiv

e su

bstra

tes

Con

sequ

ence

in th

e ca

se o

f con

duct

ive

subs

trat

esP

aral

lel m

odes

are

non

act

ive

mod

es.

Onl

y th

e vi

brat

iona

l mod

es h

avin

g a

dyna

mic

dip

ole

mom

ent c

ompo

nent

̂to

the

surfa

ce c

an b

e ob

serv

ed.

‡To

ol fo

r ana

lyzi

ng a

dsor

bate

orie

ntat

ions

HR

EELS

/ IR

spe

ctro

scop

ies

Adv

anta

ges

•Sur

face

sen

sitiv

ity (n

o ba

ckgr

ound

sub

tract

ion)

•Lar

ge s

pect

ral w

indo

ww

HR

EE

LS~

5-10

00 m

eV(4

0-80

00 c

m-1

)w

IRA

S~

75-4

50 m

eV(6

00-3

600

cm-1

)

•Mul

tiple

exc

itatio

n m

echa

nism

s‡

less

rest

rictiv

ese

lect

ion

rule

s

Dra

wba

cks

•Pla

nar &

con

duct

ive

subs

trate

s

•Poo

r res

olut

ion

DE

HR

EE

LS~

2-25

meV

(8-2

00 c

m-1

)DE

IRR

AS

~ 0.

1-0.

5m

eV(1

-4 c

m-1

)

•Ultr

a H

igh

Vac

uum

P ~

10-

9 –10

-11

Torr

(~10

-12 –

10-1

4 at

m)

•Mag

netic

shi

eldi

ng&

non

-mag

netic

co

mpo

nent

s

•Qua

ntita

tive

stud

ies

diffi

cult

W. E

rley,

J. E

lect

ron

Spe

ctro

. & R

elat

ed P

heno

men

a 44

(198

7) 6

5. R

efle

ctio

n-ab

sorp

tion

infra

red

spec

trosc

opy

of a

dsor

bate

s on

a C

u(11

1) s

ingl

e cr

ysta

l sur

face

CH

3CN

/ C

u(11

1) @

100

K

Intr

amol

ecul

ar re

actio

n -T

herm

ally

indu

ced

isom

eriz

atio

n of

m

olec

ular

sw

itche

s Au(

111)

M. P

iant

ek, G

. Sch

ulze

, M. K

och,

K.J

. Fra

nke,

F. L

eyss

ner,

A. K

rüge

r, C

. Nav

ío, J

. Mig

uel,

M.

Ber

nien

, M. W

olf,

W. K

uch,

P. T

eged

er, J

.I. P

ascu

al, J

. Am

. Che

m. S

oc. 1

31 (2

009)

127

29.

Rev

ersi

ng th

e th

erm

al s

tabi

lity

of a

mol

ecul

ar s

witc

h on

a g

old

surfa

ce: r

ing

open

ing

reac

tion

of n

itros

piro

pyra

n.

T↑

3D, i

nert,

col

orle

sspl

anar

, hig

hly

activ

e,

conj

ugat

ed, c

olor

ed

Con

text

: Eno

rmou

s ch

ange

in th

e m

olec

ular

pro

perti

es th

roug

h an

intra

mol

ecul

ar re

actio

n.‡

Sui

tabl

e to

indu

ce re

vers

ible

cha

nges

of c

hem

ical

/ op

tical

pro

perti

es o

f org

anic-

inor

gani

cin

terfa

ces,

as

part

of s

enso

rs &

det

ecto

rs, t

o pe

rform

logi

c op

erat

ions

in m

olec

ule-

base

d de

vice

s.

Mer

ocya

nine

Spi

ropy

ran

Pla

nar a

dsor

ptio

n ge

omet

ry

repo

nsib

le fo

r sta

biliz

atio

n

Intr

amol

ecul

ar re

actio

n -T

herm

ally

indu

ced

isom

eriz

atio

n of

mol

ecul

ar s

witc

hes Au

(111

)

Sub

mon

olay

er (0

.7 M

L)

T↑

M. P

iant

eket

al.,

J. A

m. C

hem

. Soc

. 131

(200

9) 1

2729

.

indo

line

benz

opyr

an

Proc

esse

s in

het

erog

eneo

us c

atal

ysis

follo

wed

ste

p by

ste

pTh

erm

ally

con

trol

led

dehy

drog

enat

ion

of N

H 3on

Ru(

11-2

0)Y

. Wan

g, K

. Jac

obi,

Sur

f. S

ci. 5

13 (2

002)

83.

Vib

ratio

nal c

hara

cter

izat

ion

of N

H a

nd N

H 2re

actio

n in

term

edia

tes

on th

e R

u(11

-20)

sur

face

.Y

. Wan

g, A

. Laf

osse

, K. J

acob

i, S

urf.

Sci

. 507

(200

2) 7

73. S

tepw

ise

dehy

drog

enat

ion

of N

H 3at

the

Ru(

11-2

0) s

urfa

ce

1stla

yer R

u2n

dla

yer R

u

Con

text

: Rea

ctio

n el

emen

tary

ste

ps ta

king

pla

ce a

t the

cat

alys

t sur

face

du

ring

the

Hab

er-B

osch

pro

cess

N2

+ 3

H2‡

2 N

H3.

‡Id

entif

icat

ion

of a

ll th

e in

volv

ed in

term

edia

te s

peci

es.

Y. W

ang

et a

l., S

urf.

Sci

. 513

(200

2) 8

3Y

. Wan

g et

al.,

Sur

f. S

ci. 5

07 (2

002)

773

Ther

mal

ly c

ontro

lled

step

wis

e de

hydr

ogen

atio

n of

NH

3at

the

Ru(

11-2

0) s

urfa

ce

1stla

yer R

u2n

dla

yer R

u

Proc

esse

s in

het

erog

eneo

us

cata

lysi

s fo

llow

ed s

tep

by

step

Y. W

ang

et a

l., S

urf.

Sci

. 513

(200

2) 8

3Y

. Wan

g et

al.,

Sur

f. S

ci. 5

07 (2

002)

773

Ther

mal

ly c

ontro

lled

step

wis

e de

hydr

ogen

atio

n of

NH

3at

the

Ru(

11-2

0) s

urfa

ce

1stla

yer R

u2n

dla

yer R

u

d s(N

H3)

Proc

esse

s in

het

erog

eneo

us

cata

lysi

s fo

llow

ed s

tep

by

step

n s,a

s(N

H3)

Sele

cted

bib

liogr

aphy

Sur

face

Sci

ence

–Fo

unda

tions

of c

atal

ysis

and

nan

osci

ence

. K.W

. Kol

asin

ski

Sur

face

Sci

ence

–A

n in

trodu

ctio

n. K

. Our

a, V

.G. L

ifshi

ts, A

.A. S

aran

in, A

.V. Z

otov

, M

. Kat

ayam

aIn

trodu

ctio

n to

sur

face

che

mis

try a

nd c

atal

ysis

. Gáb

or A

. Som

orja

iIn

trodu

ctio

n to

Sur

face

Ana

lysi

s. S

imon

J. G

arre

tt

H. O

ver,

Y.D

.Kim

, A. P

. Sei

tson

en, S

. Wen

dt, E

. Lun

dgre

n, M

. Sch

mid

, P. V

arga

, A.

Mor

gant

e, G

. Ertl

, Sci

ence

287

(545

7):1

474-

1476

(200

0)F.

Sch

reib

er,

J. P

hys.

: Con

dens

. Mat

ter 1

6 (2

004)

R88

1G

.E. P

oirie

r, C

hem

. Rev

. 97

(199

7) 1

117

Rac

hel K

. Sm

ith, P

enel

ope

A. L

ewis

, Pau

l S. W

eiss

, Pro

g. S

urf.

Sci

. 75

(200

4) 1

W. E

rley,

J. E

lect

ron

Spe

ctro

. & R

elat

ed P

heno

men

a 44

(198

7) 6

5S

.A. K

rasn

ikov

, N.N

. Ser

geev

a, Y

.N. S

erge

eva,

M.O

. Sen

ge, A

.A. C

afol

l, P

hys.

C

hem

. Che

m. P

hys.

, 201

0, 1

2, 6

666

M. P

iant

ek, G

. Sch

ulze

, M. K

och,

K.J

. Fra

nke,

F. L

eyss

ner,

A. K

rüge

r, C

. Nav

ío, J

. M

igue

l, M

. Ber

nien

, M. W

olf,

W. K

uch,

P. T

eged

er, J

.I. P

ascu

al, J

. Am

. Che

m. S

oc.

131

(200

9) 1

2729

Y. W

ang,

K. J

acob

i, S

urf.

Sci

. 513

(200

2) 8

3Y

. Wan

g, A

. Laf

osse

, K. J

acob

i, S

urf.

Sci

. 507

(200

2) 7

73

Than

kyo

ufo

ryou

ratte

ntio

n