Ultrafast dynamics of neutral superexcited Oxygen: A direct measurement of the competition between autoionization and predissociation

Using ultrafast extreme ultraviolet pulses, we performed a direct measurement of the relaxation dynamics of neutral superexcited states corresponding to the nl\sigma_g(c^4\Sigma_u^-) Rydberg series of O_2. An XUV attosecond pulse train was used to create a temporally localized Rydberg wavepacket and the ensuing electronic and nuclear dynamics were probed using a time-delayed femtosecond near-infrared pulse. We investigated the competing predissociation and autoionization mechanisms for superexcited molecules and found that autoionization is dominant for the low n Rydberg states. We measured an autoionization lifetime of 92+/-6 fs and 180+/-10 fs for (5s,4d)\sigma_g and (6s,5d)\sigma_g Rydberg state groups respectively. We determine that the disputed neutral dissociation lifetime for the \nu=0 vibrational level of the Rydberg series is 1100+/-100fs.