Articles you may be interested inThe highpressure range of the reaction of CH(2Π) with N2 High pressure range of addition reactions of HO. II. Temperature and pressure dependence of the reaction HO+COHOCO→H+CO2 High pressure range of the addition of HO to HO, NO, NO2, and CO. I. Saturated laser induced fluorescence measurements at 298 K High pressure studies of a hydrogentransfer photoreaction in a crystalline solid: Acridine/fluoreneWe report a multifaceted investigation of the hydrogen transfer photoreaction in acridine-doped fluorene crystals at higher temperature. The purpose is to elucidate the role of vibrationally assisted tunneling in this reaction system. Raman experiments were conducted at various pressures and 77 K to document the change of vibrational frequency for the promoting mode͑s͒. Upon compression, a line with a large pressure coefficient emerges from under the strong phonon mode at 96.5 cm Ϫ1 . Through polarization studies under pressure, we have identified it as a molecular butterfly mode of B 1 symmetry. We have measured the reaction rate at 150 K in order to examine the effect of a suggested promoting mode at ϳ440 cm Ϫ1 . The reaction rate again increases exponentially with pressure, but with a significantly higher pressure coefficient than that at 1.4 and 77 K. Mode patterns based on a recently published ͓J. Phys. Chem. 98, 12 223 ͑1994͔͒ normal coordinate analysis of fluorene are used to help establish the promoting modes for this reaction. This consideration suggests that the 95 and 238 cm Ϫ1 modes are likely promoting modes in addition to the 125 cm Ϫ1 libration. A computation of the Franck-Condon factor for the H-transfer process indicates that a small population of a high overtone of a promoting mode may make a disproportionally large contribution to the reaction rate. This calculation fails to account for the greater pressure coefficient of the reaction rate at higher temperature. Instead, such an increase may come partly from a greater compressibility at higher temperature.
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