The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

Abstract

The pure rotational spectrum of the CCAs radical in its ground electronic and spin state, X (2)Pi(12), has been measured using Fourier transform microwave techniques in the frequency range of 12-40 GHz. This species was created in a supersonic expansion from a reaction mixture of AsCl(3) and C(2)H(2) or CH(4) diluted in high pressure argon, using a pulsed nozzle containing a dc discharge source. Three rotational transitions were measured for the main isotopologue, (12)C(12)CAs, in the Omega=12 ladder; both lambda-doubling and arsenic (I=32) hyperfine interactions were observed in these spectra. In addition, two to four rotational transitions were recorded for the (13)C(13)CAs, (13)C(12)CAs, and (12)C(13)CAs species. In these three isotopologues, hyperfine splittings were also resolved arising from the (13)C nuclei (I=12), creating complex spectral patterns. The CCAs spectra were analyzed with a case (a) Hamiltonian, and effective rotational, lambda-doubling, and arsenic and carbon-13 hyperfine constants were determined for the Omega=12 ladder. From the effective rotational constants of the four isotopologues, an r(m) ((1)) structure has been derived with r(C-C)=1.287 A and r(C-As)=1.745 A. These bond lengths indicate that the predominant structure for arsenic dicarbide is C=C=As, with some contributing C[Triple Bond]C and C[Triple Bond]As triple bond characters. The hyperfine constants established in this work indicate that about 23 of the unpaired electron density lies on the arsenic atom, with the remaining percentage on the terminal carbon. The value of the arsenic quadrupole coupling constant (eqQ=-202 MHz) suggests that the As-C bond has a mixture of covalent and ionic characters, consistent with theoretical predictions that both pi backbonding and electron transfer play a role in creating a linear, as opposed to a cyclic, structure for certain heteroatom dicarbides.