Ion decomposition versus molecular size probed by vacuum ultraviolet photoionization.

The molecular size dependence of primary fragmentation is studied for a series of β -naphthyl esters having alkyl chain lengths from C2 to C18. The esters are vaporized at a known ftemperature and ionized by coherent vacuum ultraviolet radiation at 10.5 eV. The photoionization wavelength is energetic enough to cause both metastable and nonmetastable primary fragmentation to m / z 144, but not energetic enough to cause secondary fragmentation to m / z 115 or 116. Under these conditions, the ratio of the nonmetastable-to-metastable daughter ion current, D/m D (') is expected to give a rough indication of the average parent ion dissociation rate. The D / m D ratio decreases with increasing molecular size, but not as quickly as expected by simple RRK theory. This behavior along with temperature dependence studies suggests that the internal energy required for dissociation is provided in substantial part by both the initial thermal internal energy and the energy imparted by the photoionization step. The role of thermal energy in the dissociation of large ions is discussed.