Origin of NMR shielding in fluorides
In this work, we analyze in detail the relation between electronic structure and fluorine nuclear magnetic resonance (NMR) shielding in a series of solid state alkali fluorides (LiF, NaF, KF, RbF, and CsF). For that purpose, we use solid-state NMR calculations implemented in the density functional theory full potential WIEN2K code (APW + lo). Both measurements and calculations show that the NMR shielding varies across the series by approximately 200 ppm. We focus our discussion on an explanation of the origin of the observed trend, and we show that the variation is mainly determined by contributions from “semicore” metal-p and valence F-p bands. More specifically, the trend in fluorine shielding can be related to the small but significant change in the hybridization of these states. A second important ingredient determining the value of the shielding is the presence and position of metal-d states in the unoccupied part of the Kohn-Sham bands. Although the present analysis has been demonstrated for the 19F nucleus in alkali fluorides, the main results are more general and can explain similar trends observed in other solids and for other nuclei.
Assessment of DFT functionals with NMR chemical shifts
Density-functional theory (DFT) calculations of the magnetic shielding for nuclear magnetic resonance (NMR) in solids provide an important contribution for understanding the experimentally observed chemical shifts. It is known that the calculated NMR shielding parameters for a particular nucleus in a series of compounds correlate well with the experimentally measured chemical shifts; however, the slope of a linear fit often differs from the ideal value of 1.0. Focusing on a series of ionic compounds (fluorides, oxides, bromides, and chlorides), we show that the error is caused by the generalized gradient approximation (GGA) to the exchange-correlation functional and it is related to the well-known band-gap problem. In order to devise an ab initio approach that would correctly reproduce the variation of the shifts within a series of compounds, we test various DFT based approaches. A simple GGA+U scheme with the orbital field acting on the cation d states does not work in a general way. Also, the popular hybrid functionals (including the screened versions), which contain some fixed amount of exact exchange, lead to a large overestimation of the necessary slope correction. Surprisingly, the best solution to this problem is offered by a semilocal potential designed by Becke and Johnson to reproduce the optimized exact exchange potential in free atoms.
Intelligibility of modified speech for young listeners with normal and impaired hearing.
Exposure to modified speech has been shown to benefit children with language-learning impairments with respect to their language skills (M. M. Merzenich et al., 1998; P. Tallal et al., 1996). In the study by Tallal and colleagues, the speech modification consisted of both slowing down and amplifying fast, transitional elements of speech. In this study, we examined whether the benefits of modified speech could be extended to provide intelligibility improvements for children with severe-to-profound hearing impairment who wear sensory aids. In addition, the separate effects on intelligibility of slowing down and amplifying speech were evaluated. Two groups of listeners were employed: 8 severe-to-profoundly hearing-impaired children and 5 children with normal hearing. Four speech-processing conditions were tested: (1) natural, unprocessed speech; (2) envelope-amplified speech; (3) slowed speech; and (4) both slowed and envelope-amplified speech. For each condition, three types of speech materials were used: words in sentences, isolated words, and syllable contrasts. To degrade the performance of the normal-hearing children, all testing was completed with a noise background. Results from the hearing-impaired children showed that all varieties of modified speech yielded either equivalent or poorer intelligibility than unprocessed speech. For words in sentences and isolated words, the slowing-down of speech had no effect on intelligibility scores whereas envelope amplification, both alone and combined with slowing-down, yielded significantly lower scores. Intelligibility results from normal-hearing children listening in noise were somewhat similar to those from hearing-impaired children. For isolated words, the slowing-down of speech had no effect on intelligibility whereas envelope amplification degraded intelligibility. For both subject groups, speech processing had no statistically significant effect on syllable discrimination. In summary, without extensive exposure to the speech processing conditions, children with impaired hearing and children with normal hearing listening in noise received no intelligibility advantage from either slowed speech or envelope-amplified speech.