Observation and Calculation of the Quasibound Rovibrational Levels of the Electronic Ground State of H2+.

Although the existence of quasibound rotational levels of the X^{+} ^{2}Σ_{g}^{+}  ground state of H_{2}^{+} was predicted a long time ago, these states have never been observed. Calculated positions and widths of quasibound rotational levels located close to the top of the centrifugal barriers have not been reported either. Given the role that such states play in the recombination of H(1s) and H^{+} to form H_{2}^{+}, this lack of data may be regarded as one of the largest unknown aspects of this otherwise accurately known fundamental molecular cation. We present measurements of the positions and widths of the lowest-lying quasibound rotational levels of H_{2}^{+} and compare the experimental results with the positions and widths we calculate using a potential model for the X^{+} state of H_{2}^{+} which includes adiabatic, nonadiabatic, relativistic, and radiative corrections to the Born-Oppenheimer approximation.