1. The Complete, Temperature Resolved Spectrum Of Methyl Formate Between 214 and 265 GHz JAMES P. MCMILLAN, SARAH M. FORTMAN, CHRISTOPHER F. NEESE, and FRANK C. DE LUCIA The 70 th International Symposium on Molecular Spectroscopy June 25, 2013 The Ohio State University

2. Motivations Primary: Understand the complete contribution of each ‘Weed’ to the Astrophysical data Bonus: Obtaining Dipole Moments and Lower State Energies which may aide in QM assignments Methodology: Temperature Dependent Approach to Spectroscopy ALMA Science Verification Data “An Analysis of a Preliminary ALMA Orion KL Spectrum via the use of Complete Experimental Spectra from the Laboratory” Fortman S. M., McMillan J.P., Neese C.F., Randall S., Remijan A.J., Wilson T.L., De Lucia F.C., J.Mol.Spectrosc 280:11-20

3. Point by Point Temperature ramp, acquire 100s of spectra ~10 6 frequency bins Calibrate Temperature and Number Density for each scan Fit each frequency bin to the hundreds of scans

4. Point by Point Doppler width: More constants: Calibrate T and nL/Q Input Output Fit a single scan; multiple lines Fit a single frequency bin; all scans

5. Processing Steps Temperature Calibration Decontamination Point by Point Output Evaluation

6. Temperature Calibration Preliminary Temperatures Additional catalogs found from JPL reference pdf: Ilyushin et al. J. Mol. Spectrosc. 255 32-38 Oesterling et al. ApJ. 521 255-260. Carvajal et al. J. Mol. Spectrosc. 246 158-166 Using both vibrational states out performs using just the ground state or the 1 st excited

7. Temperature Calibration Trends in K a Tadpole Pattern Better fit with both vibrational states

8. Temperature Calibration Trends in K a Tadpole Pattern Better fit with both vibrational states

9. Temperature Calibration Trends in K a Tadpole Pattern Better fit with both vibrational states

10. Temperature Calibration Temperatures Calculated by Reference Lines 425 Spectral Scans 248-408 K over 287 minutes 346 Reference Lines JPL Catalog was used

11. Temperature Calibration Trends in K a Tadpole Pattern Better fit with both vibrational states Suggests a problems with catalog intensity Temperature Fit Residuals from Point by Point

12. Processing Steps Temperature Calibration Decontamination Point by Point Output Evaluation

13. Decontamination ‘Wheel-O-Contamination’ Untapped 210-270 data MeOH and EtCN found in Methyl Formate MeOH, EtCN, VCN already published in 210 band

14. Decontamination Find reference contaminant lines Calculate contaminant concentration for each scan Simulate contaminant signal and subtract from Methyl Formate signal

15. Decontamination Examples of Successful Contaminant Removal Blends handled well Peak intensities consistent with catalog predictions Uncontaminated regions left unaffected

16. Processing Steps Temperature Calibration Decontamination Point by Point Output Evaluation

17. Error in Energy for 408 Strongest Lines at 300K Error calculated against JPL Catalog Two red points were blended with uncatalogued lines RMS Error ~ 13.75 cm -1 Energies found by fitting:

18. Point by Point Output Evaluation - JPL Count of Lines Sorted by Intensity - Experiment JPL Catalog includes only the ground and 1 st excited vibrational states Thousands of new lines, many with nontrivial intensity. Boltzmann Factor for the first uncatalogued state

19. Summary Complete ‘Point by Point’ Spectra has been produced Systematic Trends in Temperature Fit Residuals – Potential Intensity issues in the catalogues Thousands of new lines, many with nontrivial intensity. Thanks to NASA and the NSF for funding this project.