1. First High Resolution Infrared Spectra of 2-13C-Propane
Analyses of the ν26(B2) C-Type and
ν9(A1) B-Type Bands
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

2. How This All Started: Voyager IRIS Spectra of Titan
Don Jennings/GSFC
(UT PhD Alum)
This work continued
via Cassini CIRS
data also

3. Donald’s Nicolet Data

4. Kitt Peak FT-IR Spectra

5. TDL (UTK & GSFC) & FTS (KPNO)

6. Assigning Transitions

7. 39th ISMS (1984)

8. Propane Atlas (1988)

9. Typical Atlas Page: Observed FTIR and Simulation

10. The Central Q-Branch(es) Problem: Insufficient Resolution and the State of Computing at the Time

11. - How to really get the time to do research and. solve the propane
- How to really get the time to do research and solve the propane problem? - First retire (Jan., 2015) from teaching, advising & committee duties!
- Get help from colleagues to reconnect
- Write & submit CLS proposal (Feb, 2015)
- Proposal approved May, 2015
- First Spectra taken Cycle 22
in Sept, 2015

12. Canadian Light Source (CLS)

13. View of CLS Cyclotron

14. CLS Far-IR Beamline
Brant
2m White cell
Bruker IFS 125HR

15. Help in Rebooting SJD (2014 ISMS)
Jon Hougen
Jean-Marie Flaud
Walt Lafferty

16. More Help: CLS Workshop at 2015 ISMS
Bob McKellar, Brant Billinghurst , Colin Western

17. • Sparse Spectroscopic work on Isotopologues of Propane:
Lide, MW: 1-13C & 2-13C K=0, J=0-6 (1960)
and single D substitution on 12C species
D-Substituted Only:
Henry L. McMurry, IR ( )
Friedman & Turkevich, IR (1949)
Gayles & King, IR (1965)
Kondo & Saȅki, IR Band Intensities(1973)
Gough & Murphy, Raman (1987)
ab initio
Villa, Senent & Carvajal (2013) single D and 13C

18. Flaud, Lafferty & Herman
C2v Notation Confusion
Flaud, Lafferty & Herman
Gayles & King (1965)
A1: v1 – v9 B-type
B1: v10 - v16 A-type
B2: v17 –v22 C-type
A2: v23 – v27 ia

19. So - A Cautionary Note
• Notation used here is the same as that used in Flaud,
Lafferty & Herman JCP (2001) and Villa et al. (2013)
• Mode numbering same as Shimanouchi in NBS books
• This differs from Gayles & King, Pearce & Levin and most
astronomical and other papers before 2000.
A1: v1 – v9 B-type
A2: v10 – v14 ia
B1: v15 - v21 A-type
B2: v22 –v27 C-type

20. P = 0.065 Torr; L = 72 m; Δv = 0.0009 cm-1 V26 (B2) V21 (B2) V20 (B1)
V7 (A1)
V8 (A1)

21. 2-13C-Propane ν26(B2) C-type

22. Assignment Method 1 – Plotted out small sections using Bruker
OPUS software; taped them together
to make a continuous roll
2 – Used dividers and estimated A, B,C values
to assign pQK & rQK Q-branch heads
3 – Then used dividers and estimated B bar to
find and assign corresponding P and R line
each K subband

23. 4 – Convert OPUS files to data point (x,y) files
and load into PGOPHER program
5 – Put estimated A,B,C and v0 values into
PGOPHER program and simulate spectrum
6 – Use the divider assignments to connect the
assigned observed to the simulated lines
7 – Fit lines to get better A,B,C and origin
values
8 – Extend assignments and eventually add
Centrifugal Distortion terms

24. 2-13C-Propane
V26(B2) P-Side
pQ8
pQ7
pQ6
pQ5
pQ4

25. ν26 pQ7 Q-Branch

26. pPK(J) lines

28. Residual Plot for v26 Band of 2-13C-Propane

29. Work still needing to be done on this band:
Try to assign lines from the (2v9-v9) hot band since Walter & Jean-Marie showed in their analysis of the normal propane that the 2v9 state is the perturber of the v26 Ka> 15 levels
Fit the data for v26 and 2v9 together including the A-type Coriolis coupling between these states
Produce a new simulated spectrum which can reproduce all Ka values observed in the CLS data

30. V9 (A1) B-Type Band of 2-13C-Propane
CCC Bending Mode
2-13C-Propene

31. 2-13C-Propane
V9 (A1)
pQ11
pQ10
pQ9
pQ8

32. ν9 pQ8 Q-Branch

33. 2-13C-Propane
V9(A1)
R-Side
rQ3(J)

34. v0 = ’711 (11) cm-1

35. Residual Plot for v9 Band of 2-13C-Propane

36. Ground State Constants

37. Acknowledgements UTK & Dept. of Physics & Astronomy
Canadian Light Source and its support agencies (NSERC, USask, Province of Saskatchewan)
NIST
Jon Hougen, Bob McKellar, Colin Western, Dennis Tokaryk, Scott Goudreau,