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Microwave Spectrum of the Ethanol-Water Dimer

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Presentation on theme: "Microwave Spectrum of the Ethanol-Water Dimer"— Presentation transcript:

1 Microwave Spectrum of the Ethanol-Water Dimer
Ian Finneran, Brandon Carroll, Marco Allodi, Geoffrey Blake 5:47 California Institute of Technology Brett McGuire, Marie-Aline Martin-Drumel, Michael McCarthy Harvard-Smithsonian Center for Astrophysics

2 Motivation: Hydrogen Bonding
Van der Waals Weak H-Bond Strong H-Bond C-H…π He…He C-H…O O-H…π O-H…O F-H…O <0.5 kcal/mol 0.5-4 kcal/mol 4-40 kcal/mol Pérez et al. Science (2012) 336 no pp Directional Preference

3 Thermodynamic Anomalies in Ethanol-Water
Lama, R. F., and Benjamin C-Y. Lu Journal of Chemical and Engineering Data 10.3 (1965):

4 Previous Work: Vibrational Spectra (FTIR and Raman)
“Microwave spectroscopy has unravelled the structure of the methanol–water dimer, but not of the ethanol–water dimer, to date.” Nedić, Marija, et al. "A combined Raman-and infrared jet study of mixed methanol–water and ethanol–water clusters." Physical Chemistry Chemical Physics 13.31 (2011):

5 Ab initio energy landscape
Vibrationally Corrected Optimization/vibrational frequencies mp2/aug-ccPVTZ Single point: CCSD(t)/aug-ccPVTZ

6 Caltech CP-FTMW Finneran, Ian A., et al. Review of Scientific Instruments 84.8 (2013):

7 Full Spectrum of Ethanol and Water in Argon

8 SPCAT/SPFIT (~20 ms per run per thread)
Spectral Analysis SPCAT/SPFIT (~20 ms per run per thread) Autofit Python Fitting GUI Pickett, Herbert M. "The fitting and prediction of vibration-rotation spectra with spin interactions." Journal of Molecular Spectroscopy 148.2 (1991): Seifert, NA, Finneran, IA et al. "Autofit, an automated fitting tool for broadband rotational spectra, and applications to 1-Hexanal." Journal of Molecular Spectroscopy 312 (2015):

9 Fit and Double-Resonance
Pump Check On,Off,Off,On… Single Tone On 212 111 000 Pump Check 11624 MHz Single Tone Off 11827 MHz LO = 12 GHz

10 A = MHz B = MHz C = MHz μa > μb

11

12 Kraitchman Substitution: Gauche or Trans Ethanol?
KRA Program from PROSPE

13 Extended Fit from CfA at Harvard (Balle-Flygare FTMW)
Anharmonic mp2/aug-ccPVTZ Not normalized for power yet…

14 Water and Ethanol in Helium

15 Autofit finds a new conformer of ethanol dimer!
Frequency (MHz) Experiment Ab Initio [1] A (MHz) (156) 6306.4 B (MHz) ( 99) 1171.7 C (MHz) ( 96) 1067.1 DJ (kHz) 1.5075(263) DJK (kHz) -6.447( 81) d1 (kHz) -0.211( 46) N 29 rms (kHz) 42 ΔE=39 cm-1 [1] [1] Hearn, J. Paul I., Rachel V. Cobley, and Brian J. Howard. "High-resolution spectroscopy of induced chiral dimers: A study of the dimers of ethanol by Fourier transform microwave spectroscopy." The Journal of chemical physics (2005):

16 Trans EW: In Progress

17 Extended Fit from CfA at Harvard (Balle-Flygare FTMW)
Experiment A (MHz) ( 45) B (MHz) (128) C (MHz) (120) DJ (kHz) 10.975(152)) DJK (kHz) ( 89) DK (kHz) 1.842( 45) D1 (kHz) 1.9692(276) d2 (kHz) 0.3098( 59) N 27 rms (kHz) 150 trans gauche ratio 9090 1.031 3411 0.960 2738 0.957 trans gauche ratio 9222 8940 1.032 3345 3486 0.960 2685 2778 0.967 Experiment ab initio

18 Ethanol is a better acceptor than donor Ethanol monomer favors trans
Conclusions Ethanol is a better acceptor than donor Ethanol monomer favors trans Ethanol-water favors gauche, compact structure Ground state Excited Conformer

19 Acknowledgments NSF The Blake Group

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