Conformational energy and dynamics of 9-ethylfluorene

Abstract

The S1 excited state and cation ground state of jet cooled 9-ethylfluorene have been studied experimentally using resonant enhanced multiphoton ionization and zero electron kinetic energy (ZEKE) photoelectron spectroscopy. The spectroscopy has identified two conformations of the ethyl chain which are labeled symmetric and unsymmetric both of which exist in the supersonic expansion. Density functional quantum chemical calculations are used to calculate the ground state and cation energies of each conformer as well as the barrier to conformer interconversion via a bond rotation. Dynamics on the S1 surface are measured using picosecond and nanosecond ZEKE photoelectron spectroscopy. Fast irreversible vibrational redistribution is measured at energies ⩾990 cm−1 and the ZEKE spectra are shown to have a unique signature for each of the two isomers. Picosecond and nanosecond ZEKE spectroscopy are used to search for conformer interconversion but even at the highest energy probed (2648 cm−1) no evidence is seen for a dynamic barrier crossing. Statistical density of states calculations are used to predict the relative populations of each conformer expected as a function of excess energy as well as related Rice–Ramsperger–Kassel–Marcus calculations to predict the expected isomerization rates.