TO STUDY INTERMOLECULAR INTERACTIONS IN THE DIPHENYLETHER WATER SYSTEM MARIYAM FATIMA 123 CRISTÓBAL PÉREZ 123 MELANIE SCHNELL 123 1 Max Planck Institute for the Structure and Dynamics of ID: 629004
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Slide1
BROADBAND MICROWAVE SPECTROSCOPY AS A TOOL TO STUDY INTERMOLECULAR INTERACTIONS IN THE DIPHENYLETHER - WATER SYSTEM
MARIYAM FATIMA 1,2,3, CRISTÓBAL PÉREZ1,2,3 , MELANIE SCHNELL 1,2,3
1 Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany, 2Deutsches Elektronen-Synchrotron, Hamburg, Germany 3Christian-Albrechts-Universität zu Kiel, Kiel, GermanySlide2
π
O---H
DIPHENYLETHER (DPE)Floppy moleculeTwo stable conformers (twist, skew)Most stable: twist conformerOffers two different docking sites for intermolecular interaction
2
n = 1, 2, 3
WATER
INTRODUCTION
φ
1
φ
2
t
wist
skew
φ
1
≈
φ
2
≈ 41°
φ
1
= 90°,
φ
2
= 0°
∆
E=0
kJ/
mol
∆
E=1
kJ/
molSlide3
Sample introduction
Microwave Horn Antenna (Receiver)
Microwave Horn Antenna (Emitter)
Supersonic Expansions
2-8 GHz
20 kHz
linewidth
Backing pressure of
neon:
3 bar
Temperature
for
diphenylether
: 90°
C
CHIRPED
PULSE MICROWAVE SPECTROSCOPYSlide4
4OH---OOH---
πCalculated at B3LYP-D3/aug-cc-pVTZDIPHENYLETHER
-WATER (I): AB INITIO RESULTS∆E=1.4 kJ/mol∆E=0 kJ/molSlide5
55 million acquisitions, 19 hours measurementOther lines from DPE monomer,
13C’s of DPE- water (I), DPE-water (II), DPE-water (III)DIPHENYLETHER-WATER (I): EXPERIMENTAL
RESULTSSlide6
6
State 0-
State 0+B3LYP-D3/aug-cc-pVTZMP2/6-311G++(d,p)
A(MHz)
1359.68029(42)
1362.4557(11)
1414.67
1377.04
B(MHz)
409.24121(14)
409.12297(45
)
404.91
413.82
C (MHz)
365.31297(13)
365.43020(43)
366.04
370.50
∆
J
(kHz)
0.02233(85
)
0.0235(24
)
∆
JK
(kHz)
0.2683(48)
0.263(21
)
µ
a
/µ
b
/µ
c
(D)
0.6/1.1/0.8
1.5/0.13/0.15
σ (kHz)
5.6
6.6
N
lines
a
95 (71/0/24)
78 (57/0/21)
a
The number of fitted lines.
OH---
π
DIPHENYLETHER
-
WATER (I
):
RESULTSSlide7
7
DIPHENYLETHER-WATER (I): RESULTSOH---O
Experiment (b type)B3LYP-D3/aug-cc-pVTZ
A(MHz)
1062.0824
1096.08
B(MHz)
434.2999
429.67
C (MHz)
343.60408
341.38
µ
a
/µ
b
/µ
c
(D)
1.3/2.5/0.6
N
lines
a
29
a
The number of fitted lines.
b
a
cSlide8
8
S/N ratio for DPE-water (II) is 450:1 DIPHENYLETHER-WATER (II): EXPERIMENTAL RESULTSSlide9
9DIPHENYLETHER-
WATER (II): AB INITIO RESULTS
Calculated at
B3LYP-D3/
aug
-cc-
pVTZSlide10
10DIPHENYLETHER-WATER (
II): RESULTS
ExperimentB3LYP-D3/aug-cc-pVTZA(MHz)
823.80379(24)
850.51
B(MHz)
390.51117(13)
391.08
C (MHz)
334.18534(13)
335.29
∆
J
(kHz)
0.02964(86)
∆
JK
(kHz)
0.1766(34)
∆
K
(kHz)
0.6324(47)
δ
J
0.00787(31)
δ
K
0.142(12)
µ
a
/µ
b
/µ
c
(D)
1.4/1.6/1.4
σ (kHz)
9.9
N
lines
a
294 (81/119/94)
a
The number of fitted lines.Slide11
11
DIPHENYLETHER-WATER: EXPERIMENTAL STRUCTURES
H218O measurement to find the experimental positions of waterExperimental structural positions obtained from Kraitchman method vs results from B3LYP-D3/aug-cc-pVTZSlide12
12
DIPHENYLETHER-WATER (III): EXPERIMENTAL RESULTSSlide13
13DIPHENYLETHER-
WATER (III): AB INITIO RESULTSSlide14
14DIPHENYLETHER-WATER (
III): RESULTS
Experiment
B3LYP-D3/
aug
-cc-
pVTZ
A(MHz)
621.58779(33)
651.20
B(MHz)
358.17136(13)
354.10
C (MHz)
279.70640(12)
282.18
∆
J
(kHz)
0.02406(56)
∆
K
(kHz)
0.331(11)
δ
J
(kHz)
0.00814(37)
µ
a
/µ
b/µ
c (D)
1.3/1.8/1.8
σ (kHz)
6.9
N
lines
a
190 (68/69/53)
a
The number of fitted lines.Slide15
CONCLUSION: DIPHENYLETHER-WATER
15
φ
1
= 47°
φ
2
= 35°
φ
1
= 50°
φ
2
= 31°
φ
1
= 70°
φ
2
= 19°
φ
1
= 87°
φ
2
= 7°
φ
1
φ
2
t
wist
skew
φ
1
≈
φ
2
≈ 41°
φ
1
= 90°
φ
2
= 0°
OH-
π
OH-O
DPE-water (III)
DPE-water (II)
∆
E=0
kJ/
mol
∆
E=1
kJ/
molSlide16
CONCLUSIONS AND OUTLOOK16
Identified diphenylether-water complexes up to three molecules of water.Addition of water molecule changes the structure of diphenylether from most stable twist structure to skew structure (∆E = 1kJ/mol).
Increase in the intermolecular interaction is stabilizing skew structure of diphenylether.
b
a
cSlide17
17
Sérgio
Domingos
TC03
Melanie Schnell
RG11
Cristóbal
Pérez
TE09, WG08
Benjamin Arenas
MF07
Amanda Steber
TH02
Anna
Krin
RG02
ACKNOWLEGEMENTS
Sébastien Gruet
WD07Slide18
THANK YOU