Exploring Renner-Teller Induced Quenching in the Reaction H(\u3csup\u3e2\u3c/sup\u3e\u3ci\u3eS\u3c/i\u3e)+NH(\u3ci\u3ea\u3c/i\u3e\u3csup\u3e1\u3c/sup\u3eΔ): A Combined Experimental and Theoretical Study

Abstract

Experimental rate coefficients for the removal of NH(a1Δ) and ND(a1Δ) in collisions with H and D atoms are presented; all four isotope combinations are considered: NH+H, NH+D, ND+H, and ND+D. The experiments were performed in a quasistatic laser-flash photolysis/laser-induced fluorescence system at low pressures. NH(a1Δ) and ND(a1Δ) were generated by photolysis of HN3 and DN3, respectively. The total removal rate coefficients at room temperature are in the range of (3-5) x 1013 cm3 mol-1 s-1. For two isotope combinations, NH+H and NH+D, quenching rate coefficients for the production of NH(X 3Σ-) or ND(X 3Σ-) were also determined; they are in the range of 1x1013 cm3 mol-1 s-1. The quenching rate coefficients directly reflect the strength of the Renner-Teller coupling between the 2A and 2A\u27 electronic states near linearity and so can be used to test theoretical models for describing this nonadiabatic process. The title reaction was modeled with a simple surface-hopping approach including a single parameter, which was adjusted to reproduce the quenching rate for NH+H; the same parameter value was used for all isotope combinations. The agreement with the measured total removal rate is good for all but one isotope combination. However, the quenching rates for the NH+D combination are only in fair (factor of 2) agreement with the corresponding data