High resolution spectra of the B 1Π←X 1Σ+ transition of the 39K85Rb molecule have been measured with the technique of Doppler-free optical–optical double resonance polarization spectroscopy. Molecular constants of the B 1Π(v′=0−12) levels are determined, and the RKR potential is calculated. A number of irregularities in the energies of B 1Π state levels and intensity anomalies are observed. The energy shifts of the e and f levels of the B 1Π state are studied, and the perturbations between the B 1Π and 3Σ+ states and between the B 1Π and 3Π1 states are identified. Several transitions to the 3Π1 and 3Σ+ states are also observed, and the molecular constants of the 3Π1 and 3Σ+ states are evaluated. The single rovibrational level B 1Π(v′=2, J′=41) is selectively excited by a single frequency laser chopped by an electro-optical modulator, and the decay time of the resulting fluorescence is measured at various pressures. From the Stern–Volmer plot, the radiative lifetime and the collisional cross section of the fluorescence quenching are determined to be 11.6 ns and 29 Å2, respectively. The intensity distribution of the dispersed fluorescence of the B 1Π(v′=2, J′=41)→X 1Σ+(v″=0−11, J″=42) transitions is in very good agreement with the calculated values of ν4|〈v′=2|v″〉|2. The magnitude of the transition dipole moment is determined to be 9.2 D in the range of 4.08 Å<R<4.73 Å. These results are compared with the results of recent ab initio calculations.
High-resolution spectra of the B1Π→X1Σ+ transition of 23Na85Rb molecule are measured by the technique of the Doppler-free optical–optical double resonance polarization spectroscopy (OODRPS). The molecular constants of the X1Σ+(v″=5−30) levels are determined, and the potential energy curve is constructed up to v″=30 by the RKR method. The time-resolved fluorescence intensity following the excitation to the B1Π(v′=5,J′= around 20) level is measured, and the lifetime of the B1Π(v′=5) level in collisionless limit is determined to be 17.8 ns. The absolute value of the electric dipole moment of the B1Π−X1Σ+ transition is determined to be 7.0 D in the region of 3.73 Å<R<4.98 Å. Transition lines to the (1)3Σ+ state from the B1Π(v′=8,J′=15) level, which is perturbed by the (1)3Π1(v0,N=J=15) level, are measured by the Doppler-free OODRPS. The energy spacing between the F1 and F3 components of the (1)3Σ+(v=4,N=15) level is observed to be smaller than 0.001 cm−1. The hyperfine splittings, which are described by Hund’s case (bβS), are observed, and the hyperfine constants ANa and ARb of the (1)3Σ+(v=4) level are determined to be 0.0293 and 0.0336 cm−1, respectively. The hyperfine splittings are identified as originating from the Fermi contact interaction. From the analysis, it is concluded that the electron spins in the (1)3Σ+ state are almost equally populated to the 5sRb and 3sNa orbitals.
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