State-to-State Rate Coefficients for NH3-NH3 Collisions from Pump-Probe Chirped Pulse Experiments

J Phys Chem Lett. 2019 Sep 5;10(17):4836-4841. doi: 10.1021/acs.jpclett.9b01653. Epub 2019 Aug 12.

Abstract

The kinetics of rotational inelastic NH3-NH3 collisions are recorded using pump-probe experiments, carried out with a K-band waveguide chirped pulse Fourier transform microwave spectrometer, in which the population of one inversion doublet is altered by the pump pulse. Due to self-collisions, the resulting deviation from equilibrium propagates to other states and, thus, can be interrogated by probe pulses as a function of the pump-probe delay time. A clear hierarchy of the state-to-state collision processes is found and subsequently translated into propensity rules. State-to-state rate coefficients are estimated, first via an analysis of the kinetics, and then more robustly and accurately derived from the pressure-dependent measurements using a global fitting procedure.