State-to-state reaction dynamics of R+HCN (ν1ν l 22ν3)→RH+CN( v ,  J ) with R=Cl, H

Vibrational overtone excitation of HCN in the wavelength region 6 500 cm−1–18 000 cm−1 is used to initiate the endothermic reaction of chlorine and hydrogen atoms with HCN. HCN is excited to the overtone levels (002), (004), (302), (105), and (1115). The labeling of the vibrational levels (ν1ν2l2ν3) corresponds to the normal modes ν1=CN, ν2=bend, ν3=CH, and l2=vibrational angular momentum. The product state distribution of CN(X 2Σ+) is completely analyzed by laser induced fluorescence (LIF). Excitation of the first overtone of CH-stretch leads to vibrationally excited CN in the reaction of Cl+HCN(002), implying the existence of a long living complex. The CN vibrational excitation increases with increasing H–CN stretch excitation. However, a slightly higher CN vibrational excitation is found when at the same internal energy of HCN three quanta of CN-stretch and two quanta of CH-stretch are excited. Therefore, the energy is not completely redistributed in the collision complex. The ratio of rate constants between the reactions of HCN(004) and HCN(302) with Cl is 2.8±0.6. The CN product vibrational excitation decreases again, when HCN is excited to the (105) state. At these high HCN vibrational energies the reaction mechanism seems to change toward a more direct reaction where the time left is not sufficient for energy randomization. The reaction of hydrogen with HCN(004) leads to CN-products with a similar vibrational distribution, as in the case of chlorine, but with a lower rotational excitation. The reaction H+HCN(302) shows no significant generation of CN products and a lower limit of the ratio of rate constants, k(004)/k(302)≳4, is obtained.