A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown

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A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown Low-temperature high-resolution infrared spectrum of ethane-d1, C2H5D: Rotational analysis of the ν17 band near 805 cm-1 using ERHAM P. Groner Department of Chemistry, University of Missouri - Kansas City, Kansas City, MO, USA A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA A. W. Mantz Department of Physics, Astronomy and Geophysics, Connecticut College, New London, CT, USA M. A. H. Smith Science Directorate, NASA Langley Research Center, Hampton, VA, USA International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 IR Spectrum Spectrum Details Bruker 125HR FT spectrometer at JPL Spectral range 650 - 1530 cm-1 Temperature 130.52 K Pressure 5.1 torr Cell path length 0.2038 m Resolution 0.0028 cm-1 (unapodized) Impurities CH3CH3 (≈ 2 %) International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 IR Spectrum of C2H5D Why analysis with ERHAM? * Analysis with SPFIT is quite successful (preceding presentation TG01 by Adam Daly) * Initial purpose: Analysis of 715 cm-1 band (ν11) However: ν11 level severely disturbed by 3ν18 level No useful results so far with modified ERHAM (allowing for interactions between different vibrational levels) * Therefore, try ERHAM with less perturbed ν17 at 805 cm-1 International Symposium on Molecular Spectroscopy, June 22-26, 2015

Origin of perturbations: Excited states of ν18 Torsional potential function Daly et al., J. Mol. Spectrosc. (2015) 307, 27-32 Torsional energy levels (J = 0) A state + E state + ν11, ν17 K ≠ 0 states limited by red line and A state ΔE a νobs Uncertainty νobs - νcalc Weighted residual 2A - 0A 515.1 b 1.0 2.129 2E - 0E 0.047 3E - 1E 440.1 b -2.918 3A - 1A 463.1 b 0.199 4A - 2A 336.5 b 2.192 4E - 2E 390.0 b 1.022 0E - 0A 74.167 0.018 0.000 -0.008 1E - 1A -3382.229 0.342 0.006 Coefficient This work V3 / cm-1 1004.561(44) V6 / cm-1 7.09(12) F / cm-1 (constant) 9.43489 International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 Analysis Ground state spectroscopic constants (including ρ and β) fixed to results of rotational analysis of GS and first torsional excited state ν18 [Daly et al., J. Mol. Spectrosc. (2015) 307, 27-32] ERHAM analysis based on SPFIT assignments more difficult than expected A-E splittings GS: up to ±0.0025 cm-1 ≈ unapodized resolution A-E splittings ν18 state: up to ± 0.011 cm-1 Problems * Labeling and tracking K-assignments of E levels * Inconsistencies within combination differences / upper state energies International Symposium on Molecular Spectroscopy, June 22-26, 2015

Upper state energies* / Combinations differences * Eu = El,calc + νobs Standard deviations s of Eu for a given level are typically < 0.001 cm-1 Cases with “outliers” (example for 0/A state below) Cases with 4 to 8 results spread ~ regularly over 0.002 cm-1 Cases were 6 to 10 results split into 2 groups, each group with s < 0.0004 cm-1, group separation > 0.0010 cm-1 (example for 1/E state below) σ J’ n’ J” n” ν obs Eu obs-calc average std. dev 9 5 6 796.8128 867.8080 -0.0018 8 7 807.9441 867.8100 0.0002 10 784.4464 867.8093 0.0012 1 3 797.5362 867.8117 -0.0017 2 810.9642 867.8118 -0.0016 821.2154 867.8119 784.4529 867.8121 -0.0014 807.9505 867.8132 -0.0002 796.8208 867.8134 0.0009 784.4521 867.8136 807.9499 867.8138 0.0004 867.8135 0.0003 International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 Results Weighted least squares fit Weight = inverse square of experimental uncertainty 5041 transitions assigned 2158 A-state transitions (non-zero weight) 2834 E-state transitions (non-zero weight) No frequencies assigned to more than one transition ρ ,β, & GS parameters fixed to values from rotational spectroscopy (MW to THz) [a] 1.161 weighted standard deviation (0.0006 cm-1 for most transitions) 24 variable spectroscopic constants 8 rotational & quartic centrifugal distortion constants 1 vibrational energy (805.341939(23) cm-1) 3 tunneling energy parameters 6 Coriolis-type and Dab tunneling parameters 6 tunneling contribution to rotational & quartic distortion constants [a] [Daly et al., J. Mol. Spectrosc. (2015) 307, 27-32] [a] Daly et al., J. Mol. Spectrosc. (2015) 307, 27-32 International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 Results Parameter Ground state ν17 State ρ 0.4344027(69) β (deg) 0.905(63) A (MHz) 69653.3910(24) 70183.543(18) [ga]1 (MHz) -2.842(84) B (MHz) 18859.08109(89) 18803.0694(72) [gaK]1 (MHz) 0.00320(52) C (MHz) 18214.159883(89) 18191.8103(75) [gaJ]1 (MHz) 0.00150(11) -DJ (kHz) 26.8802(18) 26.6163(18) [gb]1 (MHz) -21.5(22) -DJK (kHz) 66.3856(65) 60.178(20) [gbJ]1 (MHz) -0.0192(19) -DK (kHz) 245.155(41) 311.659(79) [Dab]1 (MHz) 5.73(26) -d1 (kHz) 1.01116(29) 0.9094(29) [A-(B+C)/2]1 /kHz 9.11(24) -44(12) d2 (kHz) 0.08252(19) 0.0656(13) [(B+C)/2]1 /kHz -1.07(16) -2.30(62) HJ (Hz) 0.0027(11) [B-C)/4]1 /kHz 0.749(91) -25.3(22) HJK (Hz) 0.2022(48) [DK]1 /kHz -0.118(60) HKJ (Hz) -0.021(31) [d1]1 /kHz 0.0266(18) HK (Hz) 4.69(18) [d2]1 /kHz 0.01006(79) ε0 (cm-1) 805.341939(23) s 1.1612 ε1 (MHz) -24.74(69) 80.13(44) ε2 (MHz) 0.0153(43) 21.62(29) ε3 (MHz) 2.26(24) International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 Discussion Satisfactory analysis of 805 cm-1 band with ERHAM Remaining problems Discrepancies of Eu, K-labeling of energy levels: need diligence ρ-vector parameters (ρ, β): fixed at GS/ν18, but could be different in ν11. LS fit with variable ρ, β: perfect correlation between ρ and ε0. Transition frequency accuracy below 0.0005 cm-1 seems possible = prerequisite to identify source of minor intensity perturbations observed in high-K R-branch transitions International Symposium on Molecular Spectroscopy, June 22-26, 2015

International Symposium on Molecular Spectroscopy, June 22-26, 2015 Thank you International Symposium on Molecular Spectroscopy, June 22-26, 2015