Microwave spectrum, structure and dipole moment of 4-fluorophenylacetylene (4FPA)

Abstract

Using a chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer, a 6-18 GHz spectrum of 4-fluorophenylacetylene (4FPA) was measured and only a-type R-branch transitions were observed up to J = 9. Rotational constants and quartic centrifugal distortion constants for the normal isotopic species were determined based on Watson-S reduction: A = 5652.812(22) MHz, B = 966.92885(11) MHz, C = 825.67680(11) MHz, D-J = 0.01377(60) kHz, and D-JK = 0.2468(61) kHz, with other three distortion constants fixed as D-K = 0.6629 kHz, d(1) = 2.386 Hz, and d(2) = 0.989 Hz from ab initio results. For six kinds of carbon-13 isotopic species, 10-15 transitions were detected by a resonant cavity FTMW spectrometer in natural abundance, and rotational constants of each species were also determined by fitting transition frequencies. Gaseous molecular structures of 4FPA were derived via the least-squares fitting (r(0)) and substitution (r(s)) methods, and ab initio optimization (r(e)). They were compared to the structures of benzene derivatives having fluorine and the acetylenic group as substituents. In addition, dipole moment component of 4FPA was also determined to be mu(a) = mu(total) = 0.8935(9) D from Stark effect measurements. (C) 2016 Elsevier B.V. All rights reserved.