1. Daniel A. Obenchain, Derek S. Frank, Stewart E. Novick,
The Position of Deuterium in HOD-N2O as Determined by Structural and Nuclear Quadrupole Coupling Constants
Daniel A. Obenchain, Derek S. Frank, Stewart E. Novick,
William Klemperer

2. Previous Microwave Study
J. Chem. Phys. 97, 2861 (1992)

3. Previous Microwave Study
MBER experiment
Measured deuterium isotopologues
Could not fully resolve the 14N hyperfine splitting
Details the internal motion of water in the complex, and compares it to the iso-electronic H2O-CO2 complex

4. Spring/Summer 2014
Michel Herman
Bill Klemperer
Stew Novick

5. A More Recent Study

6. Reported Constants from 1992 study
aZolandz, D.; Yaron, D.; Peterson, K. I.; Klemperer, W. Journal of Chemical Physics 1992, 97, 2861.

7. Where is the deuterium in HOD-N2O?or
Quasi-Parallel
Quasi-Perpendicular

8. Experiment Balle-Flygare Fourier transform microwave spectrometer
6-18GHz
1.5% N2O in at Ar was bubbled through a sample of water
H2O and D2O were combined to produce a 1:2:1 mixture of H2O:HDO:D2O

9. 212 – 111 Transition of HOD···N2O
Splitting from 4 sources
Doppler doubling
1 deuterium quadrupolar nucleus
2 nitrogen quadrupolar nuclei

10. Parameters for H2O-N2O
Previous MW Studya
This Work
State A
State B
A (MHz)
(203)
(77)
(1)
(9)
B (MHz)
(47)
(32)
(7)
(6)
C (MHz)
(47)
(32)
(5)
(3)
ΔJ (kHz)
30.8(12)
23.35(4)
23.61(3)
ΔJK (kHz)
243.0(32)
284.6(2)
283.1(1)
ΔK (kHz)
350
-206.6(6)
-213.4(3)
δJ (kHz)
8.6(3)
8.04(1)
8.685(9)
δK (kHz)d
224.2(76) -
χaa 14Ninner (kHz)
128(45)a
57(5)
65(3)
χbb 14Ninner (kHz)
-226(6)
-235(3)
χcc 14Ninner (kHz)
168(8)
169(4)
χaa 14Nouter (kHz)
371 (130)a
346(3)
344(2)
χbb 14Nouter (kHz)
-807(6)
-782(3)
χ­­cc 14Nouter (kHz)
461(6)
438(4)
N (lines) 66 58
RMS (kHz)f
4.8
2.2
aZolandz, D.; Yaron, D.; Peterson, K. I.; Klemperer, W. Journal of Chemical Physics 1992, 97, 2861.

11. HOD-N2O Hyperfine Constants
HDO-NNO
HDO-N15NO
HDO-15NNO
χaa 14Ninner (kHz) -
54(3)
χbb 14Ninner (kHz)
-279(9)
χcc 14Ninner (kHz)
225(9)
χaa 14Nouter (kHz)
319(3)
χbb 14Nouter (kHz)
-755(6)
χcc 14Nouter (kHz)
436(6)
χaa D (kHz)
-107(6)
-103(19)
χbb D (kHz)
261(9)
251(31)
χcc D (kHz)
-154(11)
-148(37)

12. HOD-N2O Hyperfine Constants
HDO-NNO
HDO-N15NO
HDO-15NNO
χaa 14Ninner (kHz)
53(7) -
54(3)
χbb 14Ninner (kHz)
-235(10)
-279(9)
χcc 14Ninner (kHz)
181(12)
225(9)
χaa 14Nouter (kHz)
332(3)
319(3)
χbb 14Nouter (kHz)
-762(4)
-755(6)
χcc 14Nouter (kHz)
430(5)
436(6)
χaa D (kHz)
-95(6)
-107(6)
-103(19)
χbb D (kHz)
230(9)
261(9)
251(31)
χcc D (kHz)
-134(11)
-154(11)
-148(37)

13. The 212 - 111 transition for HDO-14N14NO
J + IN,inner = F1
F1 + IN,outer = F2,
F2 + ID = F
F1’, F2’, F’ – F1’’, F2’’, F’’

14. HDO-N2O constants
Previous MW Studya
Previous IR Studyb
This work
HDO-NNO
HDO-N15NO
HDO-15NNO
A (MHz)
(158)
(294)
(1)
(1)
(6)
B (MHz)
(41)
(84)
(1)
(1)
(5)
C (MHz)
(41)
(92)
(5)
(1)
(5)
ΔJ (kHz)
26(2)
34.0(8)
22.18(6)
17.6(1)
18.87(5)
ΔJK (kHz)
157(19)
256(20)
207.1(2)
[207.0]
ΔK (kHz)
-111(31)
-23(57)
-115.9(7)
[-115.4]
δJ (kHz)
12.4(48)
11.0(4)
7.05(2)
[7.06]
δK (kHz)
123(32)
125(22) -
N (lines) 12 98 13 15
RMS (kHz)6
181
5.2
4.5
0.8
aZolandz, D.; Yaron, D.; Peterson, K. I.; Klemperer, W. Journal of Chemical Physics 1992, 97, 2861.
bFoldes, T.; Lauzin, C.; Vanfleteren, T.; Herman, M.; Lievin, J.; Didriche, K. Molecular Physics 2015, 113, 473.

15. Kraitchman Coordinate Determination
From Data in Originala
This Experiment
ab initio
|a|
|b| a b
H perpendicular
2.7257(5)
0.5797(5)
2.8
-0.4
H parallel
2.0949(7)
0.5703(7)
2.0929(5)
0.568(3)
1.9
0.8
N inner
0.921(2)
0.260(6)i
-0.9
0.0
N outer
1.115(2)
1.118(1)
-1.2
-1.1 a b
aZolandz, D.; Yaron, D.; Peterson, K. I.; Klemperer, W. Journal of Chemical Physics 1992, 97, 2861.

16. rm(2) Structure of H2O-N2O

17. HOD Quadrupole Tensor a b D H
Quadrupole tensor of D in DOH from Puzzarini
(units in kHz)
χ =
277.2(15)
114.7
-105.6(35)
-171.6(35)
Thaddeus, P.; Loubser, J. H. N.; Krisher, L. C. Journal of Chemical Physics 1964, 40, 257 Cazzoli, G. L., V.; Puzzarini, C. Gauss, J. In 69th International Symposium on Molecular Spectroscopy Champaign-Urbana, 2014 Puzzarini, C., hf parameters of HD(16)O, Private Communication

18. Rotation To Experimenal Valuesb a b D H
Quadrupole tensor of D in DOH from Puzzarini
(units in kHz)
χ =
277.2(15)
114.7
-105.6(35)
-171.6(35)
Quadrupole tensor of D in DOH-NNO from this work
(units in kHz)
χ =
-95(6)
230(9)
-134(11)
Rotation that reproduce experimental DOH-N2O
(units in kHz)
Rotation angles
χ =
-94
-126 38
φ = °
230
-120
θ = °
-136
χ = 0°

19. Rotation to the Perpendicular Position
Rotation to the parallel position
(units in kHz)
χ =
-94
230
-136
Quadrupole tensor of D in DOH from Puzzarini
(units in kHz)
χ =
277.2(15)
114.7
-105.6(35)
-171.6(35) a' b a b D H
Rotation to the perpendicular position
(units in kHz)
χ =
275
-103
-172

20. Observation of Perpendicular Deuterium
Herman and co-workers found a local minimum in their ab initio studies for the deuterium in the perpendicular position
7 cm-1 higher in energy than deuterium in the parallel position
Searches completed using the isotopic shifts from the rm(2) structure as a starting point
No lines found as of yet a b H D

21. Conclusion
In the HOD-N2O complex measured in by Klemperer in 1992, the measured structure was that of a deuterium occupying the quasi- parallel position
Conformation by structure fit and quadrupole tensor analysis

22. Acknowledgements
Michel Herman and his collaborators at Université Libre de Bruxelles
Cristina Puzzarini at the Università di Bologna
NSF CNS for cluster funding at Wesleyan
The Novick/Pringle/Cooke Group members