-
«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