Quantum-state-dependent decay rates of electrostatically trapped Rydberg NO molecules.

Nitric oxide (NO) molecules travelling in pulsed supersonic beams have been prepared in long-lived Rydberg-Stark states by resonance-enhanced two-colour two-photon excitation from the X Π (v'' = 0, J'' = 3/2) ground state, through the A Σ (v' = 0, N' = 0, J' = 1/2) intermediate state. These excited molecules were decelerated from 795 ms to rest in the laboratory-fixed frame of reference, in the travelling electric traps of a transmission-line Rydberg-Stark decelerator. The decelerator was operated at 30 K to minimise effects of blackbody radiation on the molecules during deceleration and trapping. The molecules were electrostatically trapped for times of up to 1 ms, and detected in situ by pulsed electric field ionisation. Measurements of the rate of decay from the trap were performed for states with principal quantum numbers between n = 32 and 50, in Rydberg series converging to the N= 0, 1, and 2 rotational states of NO. For the range of Rydberg states studied, the measured decay times of between 200 μs and 400 μs were generally observed to reduce as the value of n was increased. For some particular values of n deviations from this trend were seen. These observations are interpreted, with the aid of numerical calculations, to arise as a result of contributions to the decay rates, on the order of 1 kHz, from rotational and vibrational channel interactions. These results shed new light on the role of weak intramolecular interactions on the slow decay of long-lived Rydberg states in NO.