Vibrationally excited nitric oxide produced in the flash photolysis of nitrosyl halides

Abstract

Abstract The flash photolysis of nitrosyl chloride and nitrosyl bromide has been studied under isothermal conditions. Vibrationally excited nitric oxide molecules were produced and all levels from v" = 0 to v" = 11 were observed in absorption from the ground electronic states in the β, γ, δ and Є systems. Some of these bands have not previously been reported. The mechanism of the production is either directly NOR + hv → NO (X2II, v ≤ 11) + R(2P), or by the sequence which includes the reactions NOR + hv → NO(4II) + R, NO. 4II + M → NO (X2II, v > 0) + M In the latter case, the 4II state of NO lies not more than 3·5 eV above the ground state. Other possible mechanisms and models accounting for the direct production of vibrationally excited NO in its ground electronic states are discussed. By flashing chlorine in the presence of NOCl it was shown that the reaction Cl + NOCl → Cl2 + NO (v > 0) does not occur, thus providing direct evidence that in reactions of the type A + BCD → AB + CD only the AB molecule containing the newly formed bond can be vibrationally excited. Vibrational relaxation is very rapid and probably occurs by step-wise degradation involving resonance vibrational energy transfer. NOCl and NOBr are very efficient and with NO itself the reaction NO (v = n) + NO (v = 0) → NO (v = n-1) + NO (v = 1) can be followed.