Rovibrational characterization of X-2 Sigma(+) (BH+)-B-1 by the extrapolation of photoselected high Rydberg series in (BH)-B-11

Optical-optical-optical triple-resonance spectroscopy of (BH)-B-11 isolates high Rydberg states that form series converging to rotational state specific ionization potentials in the vibrational levels of (BH+)-B-11 from nu(+)=0 through 4. Limits defined by a comprehensive fit of these series to state-detailed thresholds yield rovibrational constants describing the X (2)Sigma(+) state of (BH+)-B-11. The data provide a first determination of the vibrational-rotational interaction parameter alpha(e)=0.4821 cm(-1) and a more accurate estimate of omega(e)=2526.58 cm(-1) together with the higher-order anharmonic terms omega(e)x(e)=61.98 cm(-1) and omega(e)y(e)=-1.989 cm(-1). The deperturbation and global fit of series to state-detailed limits also yield a precise value of the adiabatic ionization potential of (BH)-B-11 of 79 120.3 +/- 0.1 cm(-1), or 9.810 33 +/- 1x10(-5) eV. High precision is afforded here by the use of graphical analysis techniques, narrow-bandwidth laser systems, and an analysis of newly observed, high principal quantum number Rydberg states that conform well with Hund’s case (d) electron-core coupling limit. (c) 2006 American Institute of Physics.