1. 72nd International Symposium on Molecular Spectroscopy (ISMS 2017)
Investigation of the Hydantoin Monomer and its Interaction with Water Molecules
Sébastien Gruet, Cristóbal Pérez, Melanie Schnell

2. Background Detected in carbonaceous chondrites
Hydantoin
Detected in carbonaceous chondrites
Formation (glycolic acid + urea)
Shimoyama, A. and Ogasawara, R. Orig. Life Evol. Biosph. 32 (2002)
Study on interstellar ice analogues
Hydrolysis of hydantoin, under acidic conditions, can produce small amino acids.
De Marcellus et al. Astrobiology. 11, 9 (2011)
Only one work at high resolution in gas phase:
Ozeki et al. Astron. Astrophys. 600, A44 (2017)
MMW range ( GHz) - GS + 2 ES 1

3. Chirped Pulse Fourier Transform Microwave Spectrometer
« COMPACT » experiment (2-8 GHz CP-FTMW)
Oscilloscope
LNA
AWG
TWTA
Technical details
Pulse duration
FIDs acquisition
Rep. rate
Carrier gas
Backing pressure
T nozzle
4 µs
40 µs
4 Hz
neon
3 bar
≈ 180°C 2

4. Experimental Results: Hydantoin Monomer
Parameters
Theory*
Experiment
(MW)
Ozeki et al. (MMW)
A / MHz
(80)
(70)
B / MHz
(21)
(57)
C / MHz
(31)
(67)
ΔJ / kHz -
(167)
ΔJK / kHz
(69)
ΔK / kHz
(83)
δJ / kHz
(83)
δK / kHz
(144)
χaa / MHz
1.67
1.6316(56)
χbb - χcc / MHz
5.37
5.227(20)
2.75
2.5927(41)
7.44
6.935(16)
No. of lines
114
161
RMS / kHz
5.2 39
µa/ µb/ µc (D)
0.14/2.70/0
*B3LYP/aug-cc-pVTZ
Parameters
Theory*
Experiment
(MW)
Ozeki et al. (MMW)
A / MHz
(80)
(70)
B / MHz
(21)
(57)
C / MHz
(31)
(67)
ΔJ / kHz -
(167)
ΔJK / kHz
(69)
ΔK / kHz
(83)
δj / kHz
(83)
δk / kHz
(144)
χaa / MHz
1.67
1.6316(56)
χbb - χcc / MHz
5.37
5.227(20)
2.75
2.5927(41)
7.44
6.935(16)
No. of lines
114
161
RMS / kHz
5.2 39
µa/ µb/ µc (D)
0.14/2.70/0
*B3LYP/aug-cc-pVTZ
Rotational spectrum assigned (hyperfine structure resolved)
Excellent agreement with theory and literature
Complementary data for search in the ISM 3

5. Hydantoin-Water complexes
ΔE (ZPVE)
kJ mol-1 3
Hyd-H2O (3) 1 2
ΔE (ZPVE)
kJ mol-1 2
Hyd-H2O (2) 3
Lowest
Energy 1
Hyd-H2O (1) 4
ΔE (ZPVE)
kJ mol-1
Calculations: B3LYP-D3(BJ)/aug-cc-pVTZ 4

6. Hydantoin-H2O complexes: Experimental results
Hyd-H2O (1)
Hyd-H2O (2)
Hyd-H2O (3)
Parameters
Theory
Exp.
A / MHz
(60)
B / MHz
(19)
C / MHz
932.20
(16)
ΔJ / kHz
0.1344(61)
χaa / MHz
1.76
1.7106(70)
χbb - χcc / MHz
5.31
5.1876(92)
2.19
2.0803(58)
7.10
6.7808(72)
No. of lines
192
RMS / kHz
5.2
Parameters
Theory
Exp.
A / MHz
(61)
B / MHz
(48)
C / MHz
(38)
ΔJ / kHz
0.275(20)
χaa / MHz
1.46
1.4661(48)
χbb - χcc / MHz
4.89
4.8728(92)
2.71
2.5917(36)
7.25
6.7120(76)
No. of lines
184
RMS / kHz
6.2
Parameters
Theory
Exp.
A / MHz
(78)
B / MHz
(93)
C / MHz
(76)
ΔJ / kHz
0.305(42)
χaa / MHz
1.66
1.5873(14)
χbb - χcc / MHz
4.55
4.494(18)
2.37
2.1373(10)
7.87
7.346(14)
No. of lines 86
RMS / kHz
9.2 5

7. Hydantoin-H2O complexes: Experimental results6

8. Hydantoin-(H2O)2 complexes: Experimental results
Lowest Energy 1
Hyd-(H2O)2 (1)
ΔE (ZPVE)
kJ mol-1 2
Hyd-(H2O)2 (2) 1 2 3
Hyd-(H2O)2 (1)
Hyd-(H2O)2 (2)
ΔE (ZPVE)
kJ mol-1
Parameters
Theory
Exp.
A / MHz
(12)
B / MHz
765.55
(17)
C / MHz
613.12
(17)
ΔJ / kHz
0.0621(31)
ΔJK / kHz -
ΔK / kHz
-4.05(28)
δJ / kHz
χaa / MHz
1.77
1.7000(73)
χbb - χcc / MHz
5.29
5.181(13)
1.83
1.8238(66)
6.73
6.499(10)
No. of lines
218
RMS / kHz
5.9
Parameters
Theory
Exp.
A / MHz
(63)
B / MHz
969.57
(56)
C / MHz
670.81
(43)
ΔJ / kHz
0.1959(77)
ΔJK / kHz
-0.689(37)
ΔK / kHz
2.408(87)
δJ / kHz
0.0529(66)
χaa / MHz
1.17
1.2380(73)
χbb - χcc / MHz
4.62
4.625(14)
2.64
2.5276(57)
7.27
6.750(11)
No. of lines
135
RMS / kHz
7.4
Addition of water on the same binding sites as monohydrates
Good agreement with the theory
5 complexes with water assigned 7

9. Hydantoin-H218O complexes: Experimental results

10. Hydantoin-Water complexes: 18O substitution structures
2.05 Å
1.91 Å
134.2°
149.3°
2.02 Å
1.92 Å
134.4°
148.0°
2.03 Å
1.94 Å
144.0°
131.1°
1.78 Å
170.2°
1.76 Å
1.77 Å
170.3°
161.7°
1.82 Å
172.1°
1.75 Å
1.76 Å
170.1°
163.4°
Hydrogen bond
cooperativity
ΔEcoop = -19 kJ mol-1
ΔEcoop = -17 kJ mol-1 9

11. Conclusions Analyzed hyperfine structures
Complementary dataset for search in the ISM at low frequency range (MW)
Observation of 5 complexes with water
Structure confirmed by isotopic substitutions
Hydrogen bond cooperativity effects
1.78 Å
170.2°
1.76 Å
1.77 Å
170.3°
161.7°
Hydantoin-(H2O)3 complex? 10

12. Thank you for your attention!
Acknowledgment
Benjamin Arenas
MF07
Sérgio Domingos
TC03
Cristóbal Pérez
TE09, WG08
Mariyam Fatima
WD06
Melanie Schnell
RG11
Anna Krin
RG02
Amanda Steber
TH02
Thank you for your attention!