Ground state parameters of BiH 3 from infrared and millimeter-wave spectra: ground state and equilibrium structures

Abstract

Unstable, short-lived BiH 3 has been synthesized and investigated by rotational spectroscopy in the range 158 ( J=1–0) to 1280 GHz ( J=8–7). Quadrupole and spin–rotation hyperfine structures ( eQq=584.676(96) MHz), and the A 1 A 2 splitting of the K=3 ground state level, have been resolved. By merging the pure rotational data with 1764 ground state combination differences obtained from the analysis of high resolution Fourier transform infrared spectra of the ν 1– ν 4 bands [J. Mol. Spectrosc. (2004) (in press)] spanning J and K values up to 16 and 14, respectively, with 0⩽Δ K⩽9, the ground state rotational and centrifugal distortion constants up to octic and sextic terms for reductions A and B, respectively, have been determined. Of the reductions of the ground state rovibrational Hamiltonian, reduction B including ε rather than h 3 as off-diagonal element is clearly favored. An experimental r 0 structure of the very-near spherical oblate symmetric top BiH 3, r(BiH)=178.82 pm and α(HBiH)=90.320°, has been deduced from the rotational constants B 0=2.64160172(18) and C 0=2.6010403(31) cm −1. The derived experimental r e structure, r e (BiH)=177.834(50) pm and α e (HBiH)=90.321(10)°, was determined. This is in excellent agreement with the most recent ab initio structure, r e (BiH)=177.84 pm, and α e (HBiH)=90.12°.