The structure of ScC₂ (X̃²A₁): A combined Fourier transform microwave/millimeter-wave spectroscopic and computational...

Pure rotational spectra of Sc¹³C₂ (X̃²A₁) and Sc¹²C¹³C (X̃²A') have been measured using Fourier transform microwave/millimeter-wave methods. These molecules were synthesized in a DC discharge from the reaction of scandium vapor, produced via laser ablation, with ¹³CH₄ or ¹³CH₄/¹²CH₄, diluted in argon. The N_Ka,Kc = 1_0,1 → 0_0,0, 2_0,2 → 1_0,1, 3_0,3 → 2_0,2, and 4_0,4 → 3_0,3 transitions in the frequency range of 14 GHz-61 GHz were observed for both species, each exhibiting hyperfine splittings due to the nuclear spins of ¹³C (I = 1/2) and/or Sc (I = 7/2). These data have been analyzed with an asymmetric top Hamiltonian, and rotational, spin-rotation, and hyperfine parameters have been determined for Sc¹³C₂ and Sc¹²C¹³C. In addition, a quartic force field was calculated for ScC₂ and its isotopologues using a highly accurate coupled cluster-based composite method, incorporating complete basis set extrapolation, scalar relativistic corrections, outer core and inner core electron correlation, and higher-order valence correlation effects. The agreement between experimental and computed rotational constants, including the effective constant (B + C), is ∼0.5% for all three isotopologues. This remarkable agreement suggests promise in predicting rotational spectra of new transition metal-carbon bearing molecules. In combination with previous work on Sc¹²C₂, an accurate structure for ScC₂ has been established using combined experimental (B, C) and theoretical (A) rotational constants. The radical is cyclic (or T-shaped) with r_(Sc-C) = 2.048(2) Å, r_(C-C) = 1.272(2) Å, and ∠_(C-Sc-C) = 36.2(1)°. The experimental and theoretical results also suggest that ScC₂ contains a C₂ ^- moiety and is largely ionic.