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Microwave measurements of proton tunneling and structural parameters for the propiolic acid – formic acid dimer.

Published

Author(s)

Adam M. Daly, Kevin O. Douglass, Laszlo C. Sarkozy, Justin L. Neill, Matt T. Muckle, Daniel P. Zaleski, Brooks H. Pate, Stephen G. Kukolich

Abstract

Microwave spectra of the propiolic acid-formic acid, (Pro-FA) doubly hydrogen bonded complex were measured in the 1-21 GHz range. Rotational spectra for seven isotopomers were obtained and fit. For the parent isotopomer, a total of 138 a-dipole transitions and 28 b-dipole transitions were measured for which the a-dipole transitions exhibited splittings of a few MHz into pairs of lines and the b-type dipole transitions were split by approximately 580 MHz. The transitions assigned to this complex were fit to obtain rotational and distortion constants for both tunneling vibration levels. Double resonance experiments were used on some transitions to verify assignments and to obtain splittings for cases when the b-dipole transitions were difficult to measure. The experimental difference in energy between the two tunneling vibrational states is 291.428(5) MHz for proton-proton exchange and 3.35(2) MHz for the deuterium-deuterium exchange. The vibration-rotation coupling constant between the two levels, Fc, is 120.7(2) MHz for the proton-proton exchange. With one deuterium atom substituted in either of the hydrogen-bonding protons, the tunneling splittings were not observed for a-dipole transitions, supporting the assignment of the splitting to the concerted proton tunneling motion. High-level ab initio calculations provided initial rotational constants for the complex, structural parameters and some details of the proton tunneling potential energy surface. A least squares fit to the isotopic data reveal a planar structure that is slightly asymmetric in the OH distances. The formic OH•••O propiolic hydrogen bond length is 1.8 Å and the propiolic OH•••O formic hydrogen bond length is 1.6 Å, for the equilibrium configurations, The magnitude of the dipole moment was experimentally determined to be 0.579(4) D for 0+ and 0.571(7) D for 0- states.
Citation
Journal of Chemical Physics
Volume
135
Issue
15

Keywords

acid dimer, molecular spectroscopy

Citation

M., A. , Douglass, K. , Sarkozy, L. , Neill, J. , T., M. , P., D. , Pate, B. and G., S. (2011), Microwave measurements of proton tunneling and structural parameters for the propiolic acid – formic acid dimer., Journal of Chemical Physics, [online], https://doi.org/10.1063/1.3643720 (Accessed July 31, 2021)
Created October 21, 2011, Updated January 27, 2020