Rotational spectra and nitrogen nuclear quadrupole coupling for the cyanoacetylene dimer: H-C≡C-C≡N⋯H-C≡C-C≡N

Lu Kang, Philip Davis, Ian Dorell, Kexin Li, Adam Daly, Stewart E. Novick, Stephen G. Kukolich

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

The rotational spectra of cyanoacetylene dimer, H-C≡C-C≡N⋯H-C≡C-C≡N, were recorded using Balle-Flygare type Fourier transform microwave (FTMW) spectrometers. The low J transitions were measured down to 1.3 GHz at very high resolution, FWHM ∼ 1 kHz. The spectral hyperfine structure due to the 14N nuclear quadrupole coupling interactions is well-resolved below 4 GHz using a low frequency spectrometer at the University of Arizona. The experimental spectroscopic constants were fitted as: B0 = 339.2923310(79) MHz, DJ = 32.152(82) Hz, H = -0.00147(20) Hz, eqQ(14N1) = -3.9902(14) MHz, and eqQ(14N2) = -4.1712(13) MHz. The vibrationally averaged dimer configuration is H-C≡C-C≡N⋯H-C≡C-C≡N. Using a simple linear model, the vibrational ground state and the equilibrium hydrogen bond lengths are determined to be: r0(N⋯H) = 2.2489(3) Å and re(N⋯H) = 2.2315 Å. The equilibrium center-of-mass distance between the two HCCCN subunits is rcom = 7.0366 Å. Using the rigid precession model, the vibrational ground state center-of-mass distance and the pivot angles which HCCCN subunits make with the a-axis of H-C≡C-C≡N⋯H-C≡C-C≡N are rc.m. = 7.0603 Å, θ1 = 13.0°, and θ2 = 8.7°, respectively. The calculated hydrogen bond energy of H-C≡C-C≡N⋯H-C≡C-C≡N is 1466 cm-1 using the MP2/aug-cc-PVTZ method in present work.

Original languageEnglish (US)
Pages (from-to)5-12
Number of pages8
JournalJournal of Molecular Spectroscopy
Volume321
DOIs
StatePublished - Mar 1 2016

Keywords

  • Hydrogen bonding
  • Microwave spectrum
  • Quadrupole coupling

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Spectroscopy
  • Physical and Theoretical Chemistry

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