Electroreflectance spectra of Ag(111) electrodes

Electroreflectance (ER) spectra of Ag(111) evaporated electrodes on mica in aqueous electrolytes were measured within the wavelength range of 500 to 200 nm for p- and s-polarized light as a function of the angle of incidence, bias potential and surface roughness. These spectra show structures which were not seen in previously obtained ER spectra on slightly rough, polycrystalline Ag electrodes. The effect of volume and surface plasma excitation on the spectra is clearly indicated. The experimental results cannot be reproduced satisfactorily by any currently employed theoretical model which takes only free electron effects into account. The influence of the electric field on the bound electrons in the surface layer obviously cannot be neglected. It is demonstrated that the surface plasma resonance is shifted in energy by the applied electric field.     

Contribution of consonant versus vowel information to sentence intelligibility for young normal-hearing and elderly hearing-impaired listeners

The purpose of this study was to examine the contribution of information provided by vowels versus consonants to sentence intelligibility in young normal-hearing (YNH) and typical elderly hearing-impaired (EHI) listeners. Sentences were presented in three conditions, unaltered or with either the vowels or the consonants replaced with speech shaped noise. Sentences from male and female talkers in the TIMIT database were selected. Baseline performance was established at a 70 dB SPL level using YNH listeners. Subsequently EHI and YNH participants listened at 95 dB SPL. Participants listened to each sentence twice and were asked to repeat the entire sentence after each presentation. Words were scored correct if identified exactly. Average performance for unaltered sentences was greater than 94%. Overall, EHI listeners performed more poorly than YNH listeners. However, vowel-only sentences were always significantly more intelligible than consonant-only sentences, usually by a ratio of 2:1 across groups. In contrast to written English or words spoken in isolation, these results demonstrated that for spoken sentences, vowels carry more information about sentence intelligibility than consonants for both young normal-hearing and elderly hearing-impaired listeners.     

The ammonia dimer equilibrium dissociation energy: convergence to the basis set limit at the correlated level

The low-energy region of the intermolecular potential energy hypersurface (PES) of the ammonia dimer was studied at the level of second-order Moller-Plesset perturbation theory (MP2) using a very large basis set. Individual minima were located on the PES employing the counterpoise (CP) correction to account for the basis set superposition error (BSSE). Apart from these canonical MP2 calculations local MP2 (LMP2) calculations were performed. For the latter the BSSE at the correlated level is inherently absent by virtue of the local truncation of the virtual space. Results from canonical and local MP2 calculations are compared and the reliability of the LMP2 method for intermolecular complexes and clusters is discussed. The canonical MP2 calculations predicted five minimum structures, the four most stable ones lying energetically very close. For these four structures single point MP2 energy calculations with a further extended basis set (1024 functions for the ammonia dimer) were performed. The equilibrium dissociation energies so obtained are close to the one-particle basis set limit, as illustrated by a remaining BSSE of less than 0.2 kJ mol^?1. The geometry optimizations at the LMP2 level, using the three most stable canonical MP2 structures as initial geometries, all collapsed to a single minimum corresponding to an asymmetric structural arrangement. A canonical MP2 single point calculation, at that geometry, revealed that the LMP2 minimum structure is virtually as stable as the lowest minima on the canonical MP2 PES. Based on these calculations the global minimum of the ammonia dimer was assigned to a part of the PES represented by an asymmetric structure with an equilibrium dissociation energy of 13.5±0.3 kJ mol^?1