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 367.239 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

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

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

Last year we reported on some of the propane isotopomers: 2-13C-Propane: ν26 (C-Type Band) & ν9 (B-Type Band) 1-13C-Propane: ν26 (C-Type Band) & ν9 (B-Type Band) 2,2-D2-Propane: ν20 (A-Type Band)

Structure for 2-D1-Propane

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)

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

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

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

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

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

2-D1-Propane The ν9 (A1) Band CCC Bending B-Type Band Appears Unperturbed 72 m Path Res. = 0.00096 cm-1

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

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

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

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 0.0001 cm-1) 8.087 Torr 3.995 Torr

8.087 Torr 0 Shift 3.995 Torr

Ro-vibrational Constants Determined from v9 of 2-D1-Propane Ground State ab Initio1 MW Lide2 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, 10258 (2013) 2 – Lide, J. Chem. Phys. 33, 1514 (1960)

2-D1-Propane (O-C) for v9 Band All Line Fit 8116 Observations Avg. Error = 0.000273764 cm-1 2-D1-Propane (O-C) for v9 Band All Line Fit 8116 Observations

2-D1-Propane ν9 B-Type Band GSCD FIT Average Error = 0.000249627 cm-1 2-D1-Propane ν9 B-Type Band GSCD FIT 5347 Observations

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

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