Absolute absorption and fluorescence measurements over a dynamic range of 106^6 with cavity-enhanced laser-induced fluorescence

We describe a novel experimental setup that combines the advantages of both laser-induced fluorescence and cavity ring-down techniques. The simultaneous and correlated measurement of the ring-down and fluorescence signals yields absolute absorption coefficients for the fluorescence measurement. The combined measurement is conducted with the same sample in a single, pulsed laser beam. The fluorescence measurement extends the dynamic range of a stand-alone cavity ring-down setup from typically three to at least six orders of magnitude. The presence of the cavity improves the quality of the signal, in particular the signal-to-noise ratio. The methodology, dubbed cavity-enhanced laser-induced fluorescence (CELIF), is developed and rigorously tested against the spectroscopy of 1,4-bis(phenylethynyl)benzene in a molecular beam and density measurements in a cell. We outline how the method can be utilised to determine absolute quantities: absorption cross sections, sample densities and fluorescence quantum yields.Comment: 12 pages, 6 figures, submitted to J. Chem. Phy

Absolute fluorescence and absorption measurements over a dynamic range of 106 with cavity-enhanced laser-induced fluorescence

We present a novel spectroscopic technique that exhibits high sensitivity and a large dynamic range for the measurement of absolute absorption coefficients. We perform a simultaneous and correlated laser-induced fluorescence and cavity ring-down measurement of the same sample in a single pulsed laser beam. The combined measurement offers a large dynamic range and a lower limit of detection than either technique on its own. The methodology, dubbed cavity-enhanced laser-induced fluorescence, is developed and rigorously tested against the electronic spectroscopy of 1,4-bis(phenylethynyl)benzene in a molecular beam and density measurements in a cell. We outline how the method can be used to determine absolute quantities, such as sample densities, absorption cross sections, and fluorescence quantum yields, particularly in spatially confined samples

Vibrationally promoted electron emission at a metal surface: electron kinetic energy distributions

We report the first direct measurement of the kinetic energy of exoelectrons produced by collisions of vibrationally excited molecules with a low work function metal surface exhibiting electron excitations of 64% (most probable) and 95% (maximum) of the initial vibrational energy. This remarkable efficiency for vibrational-to-electronic energy transfer is in good agreement with previous results suggesting the coupling of multiple vibrational quanta to a single electron

Electron kinetic energies from vibrationally promoted surface exoemission: Evidence for a vibrational autodetachment mechanism

We report kinetic energy distributions of exoelectrons produced by collisions of highly vibrationally excited NO molecules with a low work function Cs dosed Au(111) surface. These measurements show that energy dissipation pathways involving nonadiabatic conversion of vibrational energy to electronic energy can result in electronic excitation of more than 3 eV, consistent with the available vibrational energy. We measured the dependence of the electron energy distributions on the translational and vibrational energy of the incident NO and find a clear positive correlation between final electron kinetic energy and initial vibrational excitation and a weak but observable inverse dependence of electron kinetic energy on initial translational energy. These observations are consistent with a vibrational autodetachment mechanism, where an electron is transferred to NO near its outer vibrational turning point and ejected near its inner vibrational turning point. Within the context of this model, we estimate the NO-to-surface distance for electron transfer