Communication: Vacuum ultraviolet laser photodissociation studies of small molecules by the vacuum ultraviolet laser photoionization time-sliced velocity-mapped ion imaging method.

We demonstrate that the vacuum ultraviolet (VUV) photodissociation dynamics of N2 and CO2 can be studied using VUV photoionization with time-sliced velocity-mapped ion imaging (VUV-PI-VMI) detection. The VUV laser light is produced by resonant sum frequency mixing in Kr. N2 is used to show that when the photon energy of the VUV laser is above the ionization energy of an allowed transition of one of the product atoms it can be detected and characterized as the wavelength is varied. In this case a β parameter = 0.57 for the N(2D°) was measured after exciting N2(o1Πu, v′ = 2, J′ = 2) ← N2(X1Σg+, v″ = 0, J″ = 1). Studies with CO2 show that when there is no allowed transition, an autoionization resonance can be used for the detection of a product atom. In this case it is shown for the first time that the O(1D) atom is produced with CO(1Σ+) at 92.21 nm. These results indicate that the VUV laser photodissociation combined with the VUV-PI-VMI detection is a viable method for studying the one-photon photodissociation from the ground state of simple molecules in the extreme ultraviolet and VUV spectral regions. [ABSTRACT FROM AUTHOR]