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Liquid surface studied by particle spectroscopy
Preparation of liquid surface
MIES = Metastables Induced Electron Spectroscopy
NICISS = Neutral Impact Collision Ion Scattering Spectroscopy
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NICISS (=Neutral Impact Collision Ion Scattering Spectroscopy)
Principle:
concentration depth profile
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Formamide Surface
Valence orbitals
He+, 4.5keVNICISS He+, 4.5keV-Eloss
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Formamide Surface
Valence orbitals
He+, 4.5keVNICISS He+, 4.5keV-Eloss -E
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TBPBr /FA (tetrabutylphosphonium bromide in formamide)
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NICISS (=Neutral Impact Collision Ion Scattering Spectroscopy)
CNO
PBr
0
5000
10000
15000
2 3 4 5 6 7 8
TOF [µs]
inte
nsity
[co
unts
/h/n
A]
solvent
0.01 molal
0.03 molal0.05 molal
0.20 molal0.41 molal
1.50 molal
Solution of Tetrabutylphosphonium Bromide in Formamide
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0
1000
2000
3000
4000
5000
6000
4.0 4.5 5.0 5.5 6.0 6.5 7.0TOF [µs]
inte
nsi
ty [
cou
nts
/nA
/h]
spectrum of formamide
back groundsputtered hydrogen
fit to the back ground
oxygen step
-5
0
5
10
15
20
25
30
-30 -20 -10 0 10 20 30 40
depth [Å]
conc
ent
ratio
n [1
0-3
mo
l/cm
3 ]
measurement
Gibbs dividing plane
NICISS (=Neutral Impact Collision Ion Scattering Spectroscopy)
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NICISS (=Neutral Impact Collision Ion Scattering Spectroscopy)
0
500
1000
1500
2000
2500
3000
3 3.5 4 4.5 5 5.5TOF [µs]
inte
nsi
ty [
cou
nts
/h/n
A]
solution
pure solvent
back ground of the solution ( x )
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
-30 -20 -10 0 10 20 30 40 50 60 70depth [Å]
con
cen
trat
ion
[10
-3m
ol/c
m3] Reihe1
Reihe2
Bu4P+
Br-
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POPC in HPN
POPC (=1-Palmitoyl-2-Oleoyl-SN-Glycero-3-Phosphocholine)
HPN (=3-hydroxipropionitrile)
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POPC in HPN
30
34
38
42
46
1.E-05 1.E-04 1.E-03 1.E-02
cPOPC [mol·kg-1]
[
mN
·m-1
]
0.0E+00
5.0E-11
1.0E-10
1.5E-10
2.0E-10
2.5E-10
1.0E-06 1.0E-05 1.0E-04 1.0E-03
cPOPC [mol·kg-1]
Ge
PO
PC [
mo
l/cm
2]
from surface tension
from NICISSsolute
excsolute dd G
solute
solute
soluteexcsolute
fdcd
adTR
d
lnln
ln
G
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POPC in HPN
Activity coefficient of POPC below CMC
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0.00E+00 2.00E-05 4.00E-05 6.00E-05 8.00E-05 1.00E-04 1.20E-04 1.40E-04 1.60E-04
cPOPC [mol/kg]
solutesoluteexcsolute
fdcdTR
dlnln
G
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POPC in HPN
Evaluation of the chemical potential of POPC for all concentrations
POPC / HPNchem. Potential normalized to zero at lowest POPC-concentration
y = 2239.2Ln(x) + 26210
R2 = 0.9747
0.E+00
1.E+03
2.E+03
3.E+03
4.E+03
5.E+03
6.E+03
7.E+03
8.E+03
9.E+03
1.E+04
0.E+00 2.E-04 4.E-04 6.E-04 8.E-04 1.E-03 1.E-03 1.E-03 2.E-03 2.E-03 2.E-03
nominal concentration [mol/kg]
chem
pot
entia
l [Jo
ule/
mol
]
excsolute
solute
dd
G
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POPC in HPN. Evaluation of the chemical potential of POPC.
Logarithmic plot demonstrates ideal behavior in pre-micellar range
POPC / HPNchem. Potential normalized to zero at lowest POPC-concentration
y = 2239.2Ln(x) + 26210
R2 = 0.9747
0.E+00
1.E+03
2.E+03
3.E+03
4.E+03
5.E+03
6.E+03
7.E+03
8.E+03
9.E+03
1.E+04
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02
nominal concentration [mol/kg]
che
m p
ote
ntia
l [Jo
ule
/mo
l]
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Pt clusters, embedded in IL
M rho [g/cm^3] n [mol]
Pt 195.1 19.77 6.15E-05
Polyvinylpyrrolidon 111.42 1.2 6.15E-04
BDiMIm 302.32 1.4 6.60E-04
CD3OD 36 0.847 1.65E-02
Sample from DC Knapp, Dr. Müller, Prof. Lercher, TU München
Polyvinylpyrrolidon Monomer Trimer
NO
H
HH
HH HH
H
H
NO
H
HH
HH HH
H
H
NO
H
HH
HH HH
H
HH H
NO
H
H
H
HH
HH HH
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Pt clusters, embedded in IL
M rho [g/cm^3] n [mol]
Pt 195.1 19.77 6.15E-05
Polyvinylpyrrolidon 111.42 1.2 6.15E-04
BDiMIm 302.32 1.4 6.60E-04
CD3OD 36 0.847 1.65E-02
Sample from DC Knapp, Dr. Müller, Prof. Lercher, TU München
BDiMIm= Butyl Dimethyl Imidazolium Triflat
F
F
F
S-
O
OO
NN
C+
HH
H
H
HH
H H
HH
H H
H
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Pt clusters, embedded in IL
13.9 m
solution from Dr. Müller
M rho [g/cm^3] n [mol]
Pt 195.1 19.77 6.15E-05
Polyvinylpyrrolidon 111.42 1.2 6.15E-04
BDiMIm 302.32 1.4 6.60E-04
CD3OD 36 0.847 1.65E-02
1.8 m
Preparation of thick layer:
spreading of 30 L on 4.8cm2
Preparation of thin layer:
dissolving in 8-fold amount of methanol &
spreading of 30L on 4.8cm2
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Pt clusters, embedded in IL NICISS
Pt
Pt
S
S
F
F
O
O
N
N
C
C
-500
0
500
1000
1500
2000
2500
3000
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
I korr1 (t)
selection for f it
H-recoil
steps
recoil & steps
13.9 m, 84°
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Pt clusters, embedded in IL NICISS
1.8 m, 84°
Pt
Pt
S
S
F
F
O
O
N
N
C
C
-500
0
500
1000
1500
2000
2500
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
I korr1 (t)
selection for f it
H-recoil
steps
recoil & steps
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Pt
-50
0
50
100
150
200
250
300
2.5 2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
TOF [s]
cou
nts
Pt 78°
Pt 68°
Pt 58°
Pt 48°
Pt 38°
Pt 28°
Pt 18°
Pt clusters, embedded in IL NICISS
1.8 m
Pt
Pt
S
S
F
F
O
O
N
N
C
C
-500
0
500
1000
1500
2000
2500
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
I korr1 (t)
selection for f it
H-recoil
steps
recoil & steps
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Pt
-100
0
100
200
300
400
500
600
2.5 2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
TOF [s]
cou
nts
Pt 78°
Pt 68°
Pt 58°
Pt 48°
Pt 38°
Pt 28°
Pt 18°
Pt clusters, embedded in IL NICISS
Pt
Pt
S
S
F
F
O
O
N
N
C
C
-500
0
500
1000
1500
2000
2500
3000
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
I korr1 (t)
selection for f it
H-recoil
steps
recoil & steps
13.9 m
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model consideration NICISS
surface
depth
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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surface
depth
model consideration NICISS
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Pt
-100
0
100
200
300
400
500
600
2.5 2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
TOF [s]
cou
nts
Pt 78°
Pt 68°
Pt 58°
Pt 48°
Pt 38°
Pt 28°
Pt 18°
Pt clusters, embedded in IL NICISS
13.9 m
Pt
-50
0
50
100
150
200
250
300
2.5 2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
TOF [s]
cou
nts
Pt 78°
Pt 68°
Pt 58°
Pt 48°
Pt 38°
Pt 28°
Pt 18°
1.8 m
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sample of Pt clusters, embedded in IL, goniographic NICISS
13.9 m 1.8 m
58°
-100
0
100
200
300
400
500
600
0 50 100 150 200
Fit
from exp.
78°
0
50
100
150
200
250
300
0 50 100 150 200 250 300
Reihe1
Reihe2
5%
70%
Pt concentration in bulkPt clusters
Pt atoms? percentage of this fraction is evaluated from 3D model
thin layer (~0.8nm) IL