The torsion-rotation spectrum of perchloric acid, HClO4

The rotational spectrum of HClO₄ has been observed in selected regions between 51.7 and 870 GHz. The molecule is a near spherical rotor with a moderately low barrier to internal rotation. The spectrum is characterized by strong μ_a, R-branch groupings with B + C = 5276.78 MHz. Although there are no E torsional states, the R-branches show three distinct groups of lines. There is a relatively tight cluster of symmetric rotor like transitions with K = 3n, a rather regular progression of transitions with K = 3n + 2 to high frequency and a less regular group of transitions with K = 3n + 1 to low frequency. Because the molecule is nearly spherical, the energy as a function of K is dominated by the K dependent solutions of the Mathieu equation. This unusual energy level distribution gives rise to numerous anomalous splittings and shifts due to avoided crossings within the K stacks as well as widely scattered μ_b transitions. The fitting procedure will be described and the effective parameters will be presented. Rotational transitions of excited torsional states at and above the top of the barrier and the v_t = 2-0 far infrared spectrum have been assigned. The dipole moment and the quadrupole coupling constants have been determined. Structural implications will be discussed.