1. THE ν9 (A1) B-TYPE BAND NEAR 367.239 cm−1
FIRST HIGH RESOLUTION IR SPECTRA OF 2-D1-PROPANE
THE ν9 (A1) B-TYPE BAND NEAR cm−1
Determination of Ground and Upper State Constants
Stephen J. Daunt, Robert Grzywacz
Dept. Physics & Astronomy, The University of Tennessee, Knoxville, TN
Walter J. Lafferty
Optical Technology Division, NIST, Gaithersburg, MD
Jean-Marie Flaud
Universités Paris Est Créteil et Paris Diderot, LISA, Créteil, France
Brant Billinghurst
Canadian Light Source, University of Saskatchewan, Saskatoon, SK, Canada

3. CLS Far-IR Beamline
Brant
2m White cell
Bruker IFS125 HR

4. How This All Started: Voyager IRIS Spectra of Titan
Don Jennings/GSFC
This work continued
via Cassini CIRS
data also

5. Last year we reported on some of the propane isotopomers:
2-13C-Propane: ν26 (C-Type Band) & ν9 (B-Type Band) C-Propane: ν26 (C-Type Band) & ν9 (B-Type Band)
2,2-D2-Propane: ν20 (A-Type Band)

6. Structure for 2-D1-Propane

7. Notation being used in this Presentation
The notation being used here is the same as that in Flaud, Lafferty & Herman JCP (2001) and Villa et al. PCCP (2013)
Mode numbering same as Shimanouchi in his NBS books
This differs from Gayles & King1, Pearce & Levin and most astronomical and other papers before 2000.
1J. N. Gayles, Jr. and W. T King, Spectrochim. Acta 21, 543 (1965)

8. Normal Modes for Propane 13C and D Isotopomers Titan, Saturn, other
astrophysical objects

9. The Entire IR Spectral Data Archive On These Next Two Slides!

11. from the CLS FTS Facility
C-H Stretches
New IR Survey
Spectra of
2-D1-Propane
from the CLS FTS Facility
C-D Stretch
H2O

12. 2-D1-Propane
Rocking Mode
& CC Stretch
Regions
ν26
ν13
ν21 ν8

13. The ν26 Band is Unassignable at this Time:
No Recognizable Torsional Pattern-Globally Perturbed

14. 2-D1-Propane
The ν9 (A1) Band
CCC Bending
B-Type Band
Appears
Unperturbed
72 m Path
Res. = cm-1

15. 2-D1-Propane ν9 (A1) pQ8 Q-Branch
2v9-v9
HB Q
2-D1-Propane
ν9 (A1)
pQ8 Q-Branch

16. Section of the P-Side of v9 of 2-D1-Propane
CLS Obs. Data HB HB HB
pQ12
pQ11
pQ10
PGOPHER
CALC.

17. Obs.
2-D1-Propane
ν9(A1) B-Type
rQ11 Branch
Calc.

18. From our work reported last year on bands of the 13C species it became obvious that we needed to obtain lines with high values of J and K in order to extract 6th order constants
We thus planned these experiments with much higher sample pressures
Concerns were about pressure broadening effects and most important line shifts
These next two slides show that pressure shifts were negligible
(0 to cm-1)
8.087 Torr
3.995 Torr

19. 8.087 Torr
0 Shift
3.995 Torr

20. Ro-vibrational Constants Determined from v9 of 2-D1-Propane
Ground State ab Initio1 MW Lide v9 = 1 State
4.165 e-6
-8.48 e-7
2.347 e-7
1.512 e-7
4.976 e-8
1 - Villa, Senent & Carvajal, PCCP 15, (2013)
2 – Lide, J. Chem. Phys. 33, 1514 (1960)

21. 2-D1-Propane (O-C) for v9 Band All Line Fit 8116 Observations
Avg. Error = cm-1
2-D1-Propane
(O-C) for v9 Band
All Line Fit
8116 Observations

22. 2-D1-Propane ν9 B-Type Band GSCD FIT
Average Error = cm-1
2-D1-Propane
ν9 B-Type Band
GSCD FIT
5347 Observations

23. ν9 Band Centers
2-13C
1-13C
2-D1
2,2-D2
Next Year’s
ISMS
1-D1

24. Acknowledgements
Support from the University of Tennessee - Knoxville & the Department of Physics & Astronomy
Research described in this paper was performed at the Canadian Light Source, which is supported by the Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research.
NIST
Jon Hougen, Bob McKellar, Colin Western, Dennis Tokaryk, Scott Goudreau