First High Resolution IR Spectra of 2,2-D2-Propane The v20 (B1) A-Type Band Near 964.709 cm-1. Determination of Ground and Upper State Constants Daniel Gjuraj, Department of Physics, Iona College, New Rochelle, NY, USA; Stephen J. Daunt, Robert Grzywacz, Department of Physics and Astronomy, The University of Tennessee, Knoxville, TN, USA; Walter Lafferty, Optical Technology Division, National Institute of Standards and Technology, Gaithersburg, MD, USA; Jean-Marie Flaud, CNRS, Univerités Paris Est Créteil et Paris Diderot, LISA, Créteil, France; Brant E. Billinghurst, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada;

Propane Molecule M. Villa, M. L. Senent and M. Carvajal. PCCP 15, 10258 (2013)

Fundamental frequencies of Propane Isotopes M. Villa, M. L. Senent and M. Carvajal. PCCP 15, 10258 (2013)

Fundamentals zoomed in

Discussion on non standard orientation of molecule Will get slides J. M Flaud, W. J. Lafferty, M. Herman. J. Chem. Phys. 114, 9361 (2001) J. N. Gayles, Jr. and W. T King. Spectrochim. Acta 21, 543 (1965)

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 & King, Pearce & Levin and most astronomical and other papers before 2000. J. N. Gayles, Jr. and W. T King, Spectrochim. Acta 21, 543 (1965)

Fundamental Vibrations of 2,2-D2-Propane 15*(20) Square off the 15 Most recent publish of this spectrum Add gayles and king J. N. Gayles, Jr. and W. T King. Spectrachimica Acta 21, 543 (1965)

Gayles and King had the most recent data on 2,2-D2-propane up until now J. N. Gayles, Jr. and W. T King, Spectrochim. Acta 21, 543 (1965)

Canadian Light Source (CLS)

CLS Far-IR Beamline IFS125 HR

Full Survey Scan 0.197 torr; 𝓁 = 72m; Δv = 0.0009 cm-1; 219 scans

Survey Scan of v20 (B1) for 2,2-D2- Propane

v20 (B1) A-type Band qQK(J) qPK(J) qRK(J) 10 9 8 7 6 5 4 3 1 2 3 4 5 6 1 2 3 4 5 6 7 8 9

Assignment Method Plotted out small sections using Bruker OPUS software; taped them together to make a continuous roll Used dividers and estimated A, B, C values to assign qPK & qRK J-clump features Then use dividers and estimated B bar to find and assign corresponding P and R line each K subband

Assignment Method Convert OPUS files to data point (x,y) files and load into PGOPHER program Put estimated A,B,C and v0 values into PGOPHER program and simulate spectrum Used the divider assignments to connect the assigned observed to the simulated lines Fit lines to get better A,B,C and origin values Extend assignments and eventually add Centrifugal Distortion Terms

Visual Quality of Fit 7, 6 (12) 1, 12(12) 5, 8 (12) 7, 5 (12) 8, 5 (12) 7, 5 (12) 8, 4 (12) 6, 7 (12) 5, 7 (12) 3, 8(11) 0, 12(12) 2, 9(11) 2, 11 (12) 6, 6 (12) 9, 4 (12) 9, 3 (12) 10, 3 (12) 11, 2 (12) 10, 2 (12) 11, 1 (12) 12, 1(12) 12, 0(12)

Main Hot band Region in v20 Could be anything

Slight Perturbations in v20

Global Torsional Splittings in all Other Observed Bands Small section of v26 (B2) C-type band

Central Q branch Origin located at 964.708

Residuals for v20 Band using all lines

Residuals for v20 Band using GSCD

Ground State Constants in (cm-1) for 2,2-D2- Propane

Upper State Constants

Acknowledgements Iona College Physics Department Iona College School of Arts & Science Dean’s Office UTK Department of Physics & Astronomy Canadian Light Source and its support agencies (NSERC, USask, Province of Saskatchewan) NIST