Lifetimes of partially resolved ro-vibrational levels of the Na 2Σ double well state have been measured for the first time. Ground state sodium dimer molecules in a molecular beam are resonantly excited by the doubled output of a 10 ns pulsed dye laser in the range 333-357 nm. After being allowed to decay for a predetermined time interval, the surviving excited molecules are ionized by 532 nm photons from a delayed Nd:YAG laser and detected in a linear time-of-flight mass spectrometer. By appropriate tuning of the excitation laser and systematic variation of the probe laser delay, lifetimes are obtained for vibrational levels in the range from 22 to 57. At zero rotation, the three lowest vibrational quantum numbers that we have explored (22, 25, and 28) correspond to wavefunctions whose probability densities are appreciable only in the inner well. Levels with larger quantum numbers are located above the barrier, which, for the rotation-free case, lies between quantum numbers 33 and 34. Because of the congested nature of the excitation spectrum and the experimental resolution of about 0.2 cm available to us, our experimental results are only partially quantum state resolved. Nevertheless, we can discern a decrease in lifetime from about 50 to 40 ns for the inner well levels and a slight increase in lifetime with increasing quantum number for levels above the potential barrier. We have also performed lifetime calculations based on the LEVEL and BCONT programs made available by Le Roy, the latter of which was modified by McGeehan. When limited to bound-bound transitions, theoretical lifetimes for levels above the barrier are systematically larger than experimental values by a factor of almost two. With the addition of bound-free transitions, agreement between experiment and theory is, for the most part, within the experimental uncertainties.

We report on calculations—using the LEVEL and BCONT programs by Le Roy, the latter of which is a version modified by B. McGeehan—of the dependence of the radiative lifetime of the Na2 sodium dimer 41Σg+ shelf-state on the initial vibrational and rotational level for corresponding quantum numbers of 0 ≤ v ≤ 75 and 0 ≤ J ≤ 90, respectively. We also present experimental lifetime values for 43 < v < 64, averaged over J = 19 and 21, obtained by a delayed pump-probe method using a previously described molecular beam and time-of-flight apparatus. Our calculated results are based on all possible dipole allowed transitions (to the 21Σu+, 1(B)1Πu, and 1(A)1Σu+ electronic states) terminating into bound as well as free final states. The shelf of the initial electronic state is a consequence of configuration interaction with the lowest Na+–Na− ion-pair potential and occurs, for the rotationless molecule, at the vibrational level v = 52. From the 41Σg+ vibrational ground state to the shelf, the calculated lifetimes increase monotonically by a factor of about 3.8. Beyond around v = 52, depending on rotational excitation, the lifetimes decrease, settling to a value intermediate to the maximum and the minimum at v = 0. Within error bars and in the range available, our experimental data are compatible with these findings. In addition, our calculations reveal unusual and pronounced oscillatory variation of the lifetime with rotational quantum numbers for fixed vibrational levels above—but not below—the shelf. We discuss our findings in terms of the appropriate transition dipole moments and wavefunctions and provide a detailed comparison to recent lifetime calculations of sodium dimer ion-pair states [Sanli et al., J. Chem. Phys. 143, 104304 (2015)].

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