Collisional Energy Transfer from Vibrationally Excited Hydrogen Isocyanide.

Abstract

Collisional deactivation of vibrationally excited hydrogen isocyanide (HNC) by inert gas atoms was characterized using nanosecond time-resolved Fourier transform infrared emission spectroscopy. HNC, with an average nascent internal energy of 25.9 ± 1.4 kcal mol-1, was generated following the 193 nm photolysis of vinyl cyanide (CH2CHCN) and collisionally deactivated with the series of inert atomic gases: He, Ar, Kr, and Xe. Time-dependent IR emission allows simultaneous experimental observation of the ν1 NH and ν3 NC stretch emissions from vibrationally excited HNC. Subsequent spectral fit analysis enables direct determination of the average energy of HNC in each spectrum and therefore a measure of the average energy lost per collision, ⟨ΔE⟩, as a function of internal energy. Collisional deactivation of excited HNC is shown to be relatively efficient, exhibiting ⟨ΔE⟩ values more than an order of magnitude larger than comparably sized molecules at similar internal energies. Furthermore, the lighter inert gases are shown to be more efficient quenchers. Both observations can be qualitatively explained by the momentum gap law modeled through the repulsive force dominated vibration-to-translation energy transfer mechanism. The feasibility of efficient collisional deactivation as a contributing factor to the observed overabundance of astrophysical HNC is discussed.