Vacuum ultraviolet photodissociation dynamics of N2O via the C1Π state: The N(2Dj=5/2, 3/2) + NO(X2Π) product channels

Abstract

We study the vacuum ultraviolet photodissociation dynamics of N₂O via the C¹Π state by using the time-sliced velocity map ion imaging technique. Images of N(²D_{j=5/2, 3/2}) products from the N atom elimination channels were acquired at a set of photolysis wavelengths from 142.55 to 148.19 nm. Vibrational states of the NO(X²Π) co-fragments were partially resolved in experimental images. From these images, the product total kinetic energy release distributions (TKERs), branching ratios of the vibrational states of NO(X²Π) co-fragments, and the vibrational state specific angular anisotropy parameters (<i>β</i>) have been determined. Notable features were found in the experimental results: the TKERs show that the NO(X²Π) co-fragments are highly vibrationally excited. For the highly vibrationally excited state of NO(X²Π), a bimodal rotational structure is found at all the studied photolysis wavelengths. Furthermore, the vibrational state specific <i>β</i> values of both spin-orbit channels (j = 3/2, 5/2) clearly show a monotonic decrease as the vibrational quantum number of NO(X²Π) increases. These observations suggest that multiple dissociation pathways play a role in the formation of the N(²D_{j=5/2, 3/2}) + NO(X²Π) products: one corresponds to a fast dissociation pathway through the linear state (the C¹Π state) following the initial excitation to a slightly bent geometry in the vicinity of the linear C¹Π configuration, leading to the low rotationally excited components with relatively large <i>β</i> values; the other corresponds to a relatively slow dissociation pathway through the bent C(3¹A') or C(3¹A″) state, leading to moderately rotationally excited NO(X²Π) products with smaller <i>β</i> values.