The pure rotational spectrum of ZnCl (XΣ): Variations in zinc halide bonding

The radical ZnCl (X²Σ⁺) has been studied using millimeter-wave direct-absorption techniques. Pure rotational spectra of ⁶⁷Zn³⁵Cl, ⁶⁶Zn³⁷Cl, ⁶⁸Zn³⁵Cl, ⁶⁴Zn³⁵Cl, ⁶⁴Zn³⁷Cl, and ⁶⁶Zn³⁵Cl were measured in the vibrational ground state and data were also recorded for the latter three in the v = 1 and v = 2 states. Every rotational transition was found to be split into a doublet due to spin-rotation interactions. For ⁶⁷Zn³⁵Cl, each doublet exhibited additional splittings arising from hyperfine coupling of the ⁶⁷Zn (I = 5/2) nucleus. Rotational, fine structure, and hyperfine constants have been determined from these data, and equilibrium parameters calculated. The equilibrium bond length of ⁶⁴Zn³⁵Cl is found to be 2.13003305(24) Å, in good agreement with recent theoretical predictions. Interpretation of hyperfine constants indicates that the 12σ orbital is ∼70% Zn(4s) in character, suggesting that the zinc chloride bond is relatively ionic.