Anharmonicity contributions to the vibrational second hyperpolarizability of conjugated oligomers

Restricted Hartree-Fock 6-31G calculations of electrical and mechanical anharmonicity contributions to the longitudinal vibrational second hyperpolarizability have been carried out for eight homologous series of conjugated oligomers - polyacetylene, polyyne, polydiacetylene, polybutatriene, polycumulene, polysilane, polymethineimine, and polypyrrole. To draw conclusions about the limiting infinite polymer behavior, chains containing up to 12 heavy atoms along the conjugated backbone were considered. In general, the vibrational hyperpolarizabilities are substantial in comparison with their static electronic counterparts for the dc-Kerr and degenerate four-wave mixing processes (as well as for static fields) but not for electric field-induced second harmonic generation or third harmonic generation. Anharmonicity terms due to nuclear relaxation are important for the dc-Kerr effect (and for the static hyperpolarizability) in the σ-conjugated polymer, polysilane, as well as the nonplanar π systems polymethineimine and polypyrrole. Restricting polypyrrole to be planar, as it is in the crystal phase, causes these anharmonic terms to become negligible. When the same restriction is applied to polymethineimine the effect is reduced but remains quantitatively significant due to the first-order contribution. We conclude that anharmonicity associated with nuclear relaxation can be ignored, for semiquantitative purposes, in planar π-conjugated polymers. The role of zero-point vibrational averaging remains to be evaluated

Field-induced coordinates for the determination of dynamic vibrational nonlinear optical properties

Three conjugated organic molecules that span a range of polarity and valence-bond/charge transfer characteristics were studied. It was found that dispersion can be insignificant, and that adequate treatment can be achieved with frequency-dependent field-induced vibrational coordinates (FD-FICs)

Nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties by means of electrical property expansions: Application to HF, CH4, CF4, and SF6

Electrical property derivative expressions are presented for the nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties. For CF4 and SF6, as opposed to HF and CH4, a term that is quadratic in the vibrational anharmonicity (and not previously evaluated for any molecule) makes an important contribution to the static second vibrational hyperpolarizability of CF4 and SF6. A comparison between calculated and experimental values for the difference between the (anisotropic) Kerr effect and electric field induced second-harmonic generation shows that, at the Hartree-Fock level, the nuclear relaxation/infinite frequency approximation gives the correct trend (in the series CH4, CF4, SF6) but is of the order of 50% too small

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Toward vicarious calibration of microwave remote-sensing satellites in arid environments

The Soil Moisture and Ocean Salinity (SMOS) satellite marks the commencement of dedicated global surface soil moisture missions, and the first mission to make passive microwave observations at L-band. On-orbit calibration is an essential part of the instrument calibration strategy, but on-board beam-filling targets are not practical for such large apertures. Therefore, areas to serve as vicarious calibration targets need to be identified. Such sites can only be identified through field experiments including both in situ and airborne measurements. For this purpose, two field experiments were performed in central Australia. Three areas are studied as follows: 1) Lake Eyre, a typically dry salt lake; 2) Wirrangula Hill, with sparse vegetation and a dense cover of surface rock; and 3) Simpson Desert, characterized by dry sand dunes. Of those sites, only Wirrangula Hill and the Simpson Desert are found to be potentially suitable targets, as they have a spatial variation in brightness temperatures of <4 K under normal conditions. However, some limitations are observed for the Simpson Desert, where a bias of 15 K in vertical and 20 K in horizontal polarization exists between model predictions and observations, suggesting a lack of understanding of the underlying physics in this environment. Subsequent comparison with model predictions indicates a SMOS bias of 5 K in vertical and 11 K in horizontal polarization, and an unbiased root mean square difference of 10 K in both polarizations for Wirrangula Hill. Most importantly, the SMOS observations show that the brightness temperature evolution is dominated by regular seasonal patterns and that precipitation events have only little impact.

Electro-active nanofibres electrospun from blends of poly-vinyl cinnamate and a cholesteric liquid crystalline silicone polymer

Electrospinning was used to generate polymer nanofibres from blends of poly-vinyl cinnamate (PVCN) and a cholesteric silicone polymer. Only blends that contained at least 40 % of PVCN produced fibres. Both differential scanning calorimetry and electron dispersion spectroscopy data indicate that the samples are miscible over a wide temperature interval. The variation of fibre diameter with concentration is nonlinear with a well-defined minimum corresponding to an 80 % PVCN blend. The fibres are birefringent with Kerr constants similar to that of cholesteric liquid crystals. Although not significant, the Kerr constant increases with increasing silicone polymer concentration.

When enough is not enough: information overload and metacognitive decisions to stop studying information

People are often exposed to more information than they can actually remember. Despite this frequent form of information overload, little is known about how much information people choose to remember. Using a novel “stop” paradigm, the current research examined whether and how people choose to stop receiving new—possibly overwhelming—information with the intent to maximize memory performance. Participants were presented with a long list of items and were rewarded for the number of correctly remembered words in a following free recall test. Critically, participants in a stop condition were provided with the option to stop the presentation of the remaining words at any time during the list, whereas participants in a control condition were presented with all items. Across five experiments, we found that participants tended to stop the presentation of the items to maximize the number of recalled items, but this decision ironically led to decreased memory performance relative to the control group. This pattern was consistent even after controlling for possible confounding factors (e.g., task demands). The results indicated a general, false belief that we can remember a larger number of items if we restrict the quantity of learning materials. These findings suggest people have an incomplete understanding of how we remember excessive amounts of information.

I owe you: age-related similarities and differences in associative memory for gains and losses

Older adults often experience associative memory impairments but can sometimes remember important information. The current experiments investigate potential age-related similarities and differences associate memory for gains and losses. Younger and older participants were presented with faces and associated dollar amounts, which indicated how much money the person “owed” the participant, and were later given a cued recall test for the dollar amount. Experiment 1 examined face-dollar amount pairs while Experiment 2 included negative dollar amounts to examine both gains and losses. While younger adults recalled more information relative to older adults, both groups were more accurate in recalling the correct value associated with high value faces compared to lower value faces and remembered gist-information about the values. However, negative values (losses) did not have a strong impact on recall among older adults versus younger adults, illustrating important associative memory differences between younger and older adults.

Metacognition and proofreading: the roles of aging, motivation, and interest

Objectives: The current study examined younger and older adults’ error detection accuracy, prediction calibration, and postdiction calibration on a proofreading task, to determine if age-related difference would be present in this type of common error detection task. Method: Participants were given text passages, and were first asked to predict the percentage of errors they would detect in the passage. They then read the passage and circled errors (which varied in complexity and locality), and made postdictions regarding their performance, before repeating this with another passage and answering a comprehension test of both passages. Results: There were no age-related differences in error detection accuracy, text comprehension, or metacognitive calibration, though participants in both age groups were overconfident overall in their metacognitive judgments. Both groups gave similar ratings of motivation to complete the task. The older adults rated the passages as more interesting than younger adults did, although this level of interest did not appear to influence error-detection performance. Discussion: The age equivalence in both proofreading ability and calibration suggests that the ability to proofread text passages and the associated metacognitive monitoring used in judging one’s own performance are maintained in aging. These age-related similarities persisted when younger adults completed the proofreading tasks on a computer screen, rather than with paper and pencil. The findings provide novel insights regarding the influence that cognitive aging may have on metacognitive accuracy and text processing in an everyday task.

Influence of dentin cavity surface finishing on micro-tensile bond strength of adhesives

The current trend toward minimal-invasive dentistry has introduced innovative techniques for cavity preparation. Chemical vapor deposition (CVD) and laser-irradiation technology have been employed as an alternative to the common use of regular burs in high-speed turbines. Objectives. The purpose of this study was to assess the influence of alternative techniques for cavity preparation on the bonding effectiveness of different adhesives to dentin, and to evaluate the morphological characteristics of dentin prepared with those techniques. Methods. One etch&rinse adhesive (OptiBond FL, Kerr) and three self-etch systems (Adper Prompt L-Pop, 3M ESPE; Clearfil SE Bond, Kuraray; Clearfil S3 Bond, Kuraray) were applied on dentin prepared with a regular bur in a turbine, with a CVD bur in a turbine, with a CVD tip in ultrasound and with an ErCr:YSGG laser. The micro-tensile bond strength (mu TBS) was determined after storage in water for 24 h at 37 degrees C, and morphological evaluation was performed by means of field -emission -gun scanning electron microscopy (Feg-SEM). Results. Feg-SEM evaluation revealed different morphological features on the dentin surface after the usage of both the conventional and alternative techniques for cavity preparation, more specifically regarding smear-layer thickness and surface roughness. CVD bur-cut, CVD ultra-sonoabraded and laser-irradiated dentin resulted in lower mu TBSs than conventionally bur-cut dentin, irrespective of the adhesive employed. Significance. The techniques, such as CVD diamond-bur cutting, CVD diamond ultra-sonoabrasion and laser-irradiation, used for cavity preparation may affect the bonding effectiveness of adhesives to dentin, irrespective of their acidity or approach. (C) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.