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Branching ratios for N( 2 D 0 3/2 ) and N( 2 D 0 5/2 ) produced by predissociation of state selected excited nitrogen molecules in the vacuum ultraviolet region have been measured for the first time. The quantum numbers of the excited nitrogen molecule are defined by selective excitation of the nitrogen molecule in the Franck-Condon region from the ground electronic, 1 Σ g + , vibrational, v″, and rotational, J″ state to an excited E u ', v', J' state with a tunable vacuum ultraviolet, VUV 1 , laser. The neutral atoms produced by predissociation from this excited state are then selectively ionized with a second tunable VUV 2 laser. Measurement of the relative populations of these two atoms formed in their spin-orbit states defines the quantum states for the atomic products. This means that the wave functions of the initial state and knowledge of the relative yields define all the experimental parameters for this series of unimolecular reactions. The ions formed by VUV 2 are mass analyzed with a time-of-flight mass spectrometer and detected with a time slice velocity ion imaging mass spectrometer. In this manner, we can determine the recoil velocity associated with the predissociation process. Two different techniques are used to determine the spin-orbit ratios, namely, resonant VUV photoionization (RVUV-PI) spectroscopy and total kinetic energy release (TKER) spectroscopy determined from the image produced when the atoms are selectively ionized by VUV 2 in the interaction region. The TKER spectra obtained from the lines at 110 296.25 and 110 304.96 cm -1 that couple to a newly discovered autoionization line at 129 529.4255 ± 0.0015 cm -1 prove that the lines observed in this region originate from the N( 2 D 0 3/2 S 2 D 0 5/2 ) atoms. Two other lines in this region at 110 286.20 and 110 299.89 cm -1 originate from the nitrogen N( 4 S 0 3/2 ) that is photoionized in a 1+ 1 VUV-UV resonant multiphoton ionization process. The spin-orbit branching ratios have been evaluated for valence and Rydberg electronic excited states from 104 129.4 to 118 772.1 cm -1 , and it shows that they are independent of the rotational and vibrational quantum numbers. They are not appreciably affected by the symmetry properties of the wave function in the Franck-Condon region of the excited states. In the energy region below 117 153.8 cm -1 the pathways at long internuclear distances appear to determine [N( 2 D 0 3/2 )]/[N( 2 D 0 5/2 )] branching ratios of ∼0.38, ∼0.62, and ∼1.04. At higher energies, TKER and RVUV-PI spectroscopy have been used to show that the average fraction of the N( 2 D 0 3/2 ) and N( 2 D 0 5/2 ) atoms produced in the spin-allowed channels that produce two N( 2 D 0 J ) is 0.85 versus 0.15 for spin-forbidden channels. The importance and need for this information for comparison with theory and applications in astrochemistry are briefly discussed.

Collisional removal of electronic energy from O 2 in the low-lying a 1 Δ g state is typically an extremely slow process for the v = 0 level. In this study, we report results on the deactivation of O 2 ( a 1 Δ g , v = 1-3) in collisions with O 2 and CO 2 . Ozone photodissociation in the 200-310 nm Hartley band is the source of O 2 ( a, v), and resonance-enhanced multiphoton ionization is used to probe the vibrational-level populations. Deactivation of the a( v = 1-3) levels in collisions with O 2 at 300 K is fast, with rate coefficients of (5.6 ± 1.1) × 10 -11 , (3.6 ± 0.4) × 10 -11 , and (1.9 ± 0.4) × 10 -11 cm 3 s -1 (2σ) for v = 1, 2, and 3, respectively. The relaxation process appears to involve a near-resonant electronic energy transfer pathway analogous to that observed in vibrationally excited O 2 ( b 1 Σ g + ). With CO 2 collider gas, the removal rate coefficient at 300 K is (1.8 ± 0.4) × 10 -14 and (4.4 ± 0.6) × 10 -14 s 3 s -1 (2σ) for v = 1 and 2, respectively. Despite the small mole fraction of O 2 in the atmospheres of Mars and Venus, O 2 is at least as important as CO 2 in the final stages of collisional relaxation within the O 2 vibrational-level manifold.