Low temperature rate constants for the N(4S) + CH(X2{\Pi}r) reaction. Implications for N2 formation cycles in dense interstellar clouds

TL;DR

This study combines experimental measurements and quantum calculations to determine low-temperature rate constants for the N(4S) + CH reaction, revealing a positive temperature dependence and impacting models of N2 formation in dense interstellar clouds.

Contribution

It provides the first combined experimental and theoretical analysis of the N + CH reaction at low temperatures, improving understanding of interstellar nitrogen chemistry.

Findings

Rate constants increase with decreasing temperature.

Quantum calculations agree with experimental data.

N2 formation models predict 10-20% lower abundances.

Abstract

Rate constants for the potentially important interstellar N(4S) + CH(X2{\Pi}r) reaction have been measured in a continuous supersonic flow reactor over the range 56 K < T < 296 K using the relative rate technique employing both the N(4S) + OH(X2{\Pi}i) and N(4S) + CN(X2{\Sigma}+) reactions as references. Excess concentrations of atomic nitrogen were produced by the microwave discharge method upstream of the Laval nozzle and CH and OH radicals were created by the in-situ pulsed laser photolysis of suitable precursor molecules. In parallel, quantum dynamics calculations of the title reaction have been performed based on accurate global potential energy surfaces for the 13A' and 13A" states of HCN and HNC, brought about through a hierarchical construction scheme. Both adiabatic potential energy surfaces are barrierless, each one having two deep potential wells suggesting that this reaction is dominated by a complex-forming mechanism. The experimental and theoretical work are inexcellent agreement, predicting a positive temperature dependence of the rate constant, in contrast to earlier experimental work at low temperature. The effects of the new low temperature rate constants on interstellar N2 formation are tested using a dense cloud model, yielding N2 abundances 10-20 % lower than previously predicted.