Microwave structure for the propiolic acid-formic acid complex

Stephen G. Kukolich, Erik G. Mitchell, Spencer J. Carey, Ming Sun, Bryan A. Sargus

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

New microwave spectra were measured to obtain rotational constants and centrifugal distortion constants for the DCCCOOH⋯HOOCH and HCCCOOD⋯DOOCH isotopologues. Rotational transitions were measured in the frequency range of 4.9-15.4 GHz, providing accurate rotational constants, which, combined with previous rotational constants, allowed an improved structural fit for the propiolic acid-formic acid complex. The new structural fit yields reasonably accurate orientations for both the propiolic and formic acid monomers in the complex and more accurate structural parameters describing the hydrogen bonding. The structure is planar, with a positive inertial defect of Δ = 1.33 amu Å2. The experimental structure exhibits a greater asymmetry for the two hydrogen bond lengths than was obtained from the ab initio mp2 calculations. The best-fit hydrogen bond lengths have an r(O1-H1⋯O4) of 1.64 Å and an r(O3-H2⋯O2) of 1.87 Å. The average of the two hydrogen bond lengths is rav(exp) = 1.76 Å, in good agreement with rav(theory) = 1.72 Å. The center of mass separation of the monomers is RCM = 3.864 Å. Other structural parameters from the least-squares fit using the experimental rotational constants are compared with theoretical values. The spectra were obtained using two different pulsed beam Fourier transform microwave spectrometers.

Original languageEnglish (US)
Pages (from-to)9525-9530
Number of pages6
JournalJournal of Physical Chemistry A
Volume117
Issue number39
DOIs
StatePublished - Oct 3 2013

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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