Relaxation and derelaxation of pure and hydrogenated amorphous silicon during thermal annealing experiments

The structural relaxation of pure amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) materials, that occurs during thermal annealing experiments, has been analyzed by Raman spectroscopy and differential scanning calorimetry. Unlike a-Si, the heat evolved from a-Si:H cannot be explained by relaxation of the Si-Si network strain but it reveals a derelaxation of the bond angle strain. Since the state of relaxation after annealing is very similar for pure and hydrogenated materials, our results give strong experimental support to the predicted configurational gap between a-Si and crystalline silicon

Simple finite field nuclear relaxation method for calculating vibrational contribution to degenerate four-wave mixing

A simple extended finite field nuclear relaxation procedure for calculating vibrational contributions to degenerate four-wave mixing (also known as the intensity-dependent refractive index) is presented. As a by-product one also obtains the static vibrationally averaged linear polarizability, as well as the first and second hyperpolarizability. The methodology is validated by illustrative calculations on the water molecule. Further possible extensions are suggested

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

The effect of counterpoise correction and relaxation energy term to the internal rotation barriers: application to the BF3 ...NH3 and C2H4 ...SO2 dimers

The relevance of the fragment relaxation energy term and the effect of the basis set superposition error on the geometry of the BF3⋯NH3 and C2H4⋯SO2 van der Waals dimers have been analyzed. Second-order Møller-Plesset perturbation theory calculations with the d95(d,p) basis set have been used to calculate the counterpoise-corrected barrier height for the internal rotations. These barriers have been obtained by relocating the stationary points on the counterpoise-corrected potential energy surface of the processes involved. The fragment relaxation energy can have a large influence on both the intermolecular parameters and barrier height. The counterpoise correction has proved to be important for these systems

A new all-round density functional based on spin states and SN2 barriers

We report here a new empirical density functional that is constructed based on the performance of OPBE and PBE for spin states and SN 2 reaction barriers and how these are affected by different regions of the reduced gradient expansion. In a previous study [Swart, Sol̀, and Bickelhaupt, J. Comput. Methods Sci. Eng. 9, 69 (2009)] we already reported how, by switching between OPBE and PBE, one could obtain both the good performance of OPBE for spin states and reaction barriers and that of PBE for weak interactions within one and the same (SSB-sw) functional. Here we fine tuned this functional and include a portion of the KT functional and Grimme's dispersion correction to account for π- π stacking. Our new SSB-D functional is found to be a clear improvement and functions very well for biological applications (hydrogen bonding, π -π stacking, spin-state splittings, accuracy of geometries, reaction barriers)

Social perception gaze patterns, symptom severity and resting brain function measured using Arterial Spin Labelling

Autistic spectrum disorder (ASD) is characterised by qualitative alterations in reciprocal social interactions. Some recent studies show alterations in gaze patterns during social perception and rest-functional abnormalities in the ‘social brain network’. This study investigated: i) social perception gaze patterns in children with ASD and controls, ii) the relationship between autism clinical severity and social perception gaze patterns, iii) the relationship between resting cerebral blood flow (rCBF) and social perception gaze patterns. Methods: Nine children with ASD and 9 children with typical development were studied. Eye-tracking was used to detect gaze patterns during presentation of stimuli depicting social scenes. Autism clinical severity was established using the Autism Diagnostic Interview Revised (ADI-R). Arterial spin labelling MRI was used to quantify rCBF. Results: The ASD group looked less at social regions and more at non-social regions than controls. No significant correlation was found between ASD clinical severity and social perception gaze patterns. In the ASD group, gaze behaviour was related to rCBF in the temporal lobe regions at trend level. Positive correlations were found between temporal rCBF and gaze to the face region, while negative correlations were found between temporal rCBF and gaze to non-social regions. Conclusions: These preliminary results suggest that social perception gaze patterns are altered in children with ASD, and could be related to temporal rCBF.

Significance of cross correlations in the stress relaxation of polymer melts

According to linear response theory, all relaxation functions in the linear regime can be obtained using time correlation functions calculated under equilibrium. In this paper, we demonstrate that the cross correlations make a significant contribution to the partial stress relaxation functions in polymer melts. We present two illustrations in the context of polymer rheology using (1) Brownian dynamics simulations of a single chain model for entangled polymers, the slip-spring model, and (2) molecular dynamics simulations of a multichain model. Using the single chain model, we analyze the contribution of the confining potential to the stress relaxation and the plateau modulus. Although the idea is illustrated with a particular model, it applies to any single chain model that uses a potential to confine the motion of the chains. This leads us to question some of the assumptions behind the tube theory, especially the meaning of the entanglement molecular weight obtained from the plateau modulus. To shed some light on this issue, we study the contribution of the nonbonded excluded-volume interactions to the stress relaxation using the multichain model. The proportionality of the bonded/nonbonded contributions to the total stress relaxation (after a density dependent "colloidal" relaxation time) provides some insight into the success of the tube theory in spite of using questionable assumptions. The proportionality indicates that the shape of the relaxation spectrum can indeed be reproduced using the tube theory and the problem is reduced to that of finding the correct prefactor. (c) 2007 American Institute of Physics

Spin spaces and positive decomposition of linear maps on ordered Banach spaces

Spin factors and generalizations are used to revisit positive generation of B(E, F), where E and F are ordered Banach spaces. Interior points of B(E, F)+ are discussed and in many cases it is seen that positive generation of B(E, F) is controlled by spin structure in F when F is a JBW-algebra.

A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

Stress relaxation behaviour of frozen sucrose solutions

The stress relaxation behaviour of two frozen sucrose solutions (7% and 19%) during indentation in the temperature range of -20C to -40C were investigated. The stress relaxation is similar to that of pure polycrystalline ice, which is controlled by steady-state creep. The steady state creep rate exponent, m, of 7% and 19% sucrose solutions lies between 2.3 and 3.6. The steady state creep rate constant, B, of 19% sucrose solution is greater than that of 7% sucrose solution. It is suggested that the steady-state creep rate exponent m depends on contributions from the proportions of favourably oriented grains, unfavourably oriented grains and grain boundaries to creep and that these components depend on the value of internal stress which is related to the hardness of samples at the different testing temperatures. The steady-state creep rate constant B depends on the mobility of dislocations in sucrose solutions which, in turn, depends on the temperature and the concentration of sucrose.

Stress relaxation behavior of wheat dough, gluten, and gluten protein fractions

Relaxation behavior was measured for dough, gluten and gluten protein fractions obtained from the U.K. biscuitmaking flour, Riband, and the U.K. breadmaking flour, Hereward. The relaxation spectrum, in which relaxation times (tau) are related to polymer molecular size, for dough showed a broad molecular size distribution, with two relaxation processes: a major peak at short times and a second peak at times longer than 10 sec, which is thought to correspond to network structure, and which may be attributed to entanglements and physical cross-links of polymers. Relaxation spectra of glutens were similar to those for the corresponding doughs from both flours. Hereward gluten clearly showed a much more pronounced second peak in relaxation spectrum and higher relaxation modulus than Riband gluten at the same water content. In the gluten protein fractions, gliadin and acetic acid soluble glutenin only showed the first relaxation process, but gel protein clearly showed both the first and second relaxation processes. The results show that the relaxation properties of dough depend on its gluten protein and that gel protein is responsible for the network structure for dough and gluten.

Receding and disparity cues aid relaxation of accommodation

Purpose. Accommodation can mask hyperopia and reduce the accuracy of non-cycloplegic refraction. It is, therefore, important to minimize accommodation to obtain a measure of hyperopia as accurate as possible. To characterize the parameters required to measure the maximally hyperopic error using photorefraction, we used different target types and distances to determine which target was most likely to maximally relax accommodation and thus more accurately detect hyperopia in an individual. Methods. A PlusoptiX SO4 infra-red photorefractor was mounted in a remote haploscope which presented the targets. All participants were tested with targets at four fixation distances between 0.3 and 2 m containing all combinations of blur, disparity, and proximity/looming cues. Thirty-eight infants (6 to 44 weeks) were studied longitudinally, and 104 children [4 to 15 years (mean 6.4)] and 85 adults, with a range of refractive errors and binocular vision status, were tested once. Cycloplegic refraction data were available for a sub-set of 59 participants spread across the age range. Results. The maximally hyperopic refraction (MHR) found at any time in the session was most frequently found when fixating the most distant targets and those containing disparity and dynamic proximity/looming cues. Presence or absence of blur was less significant, and targets in which only single cues to depth were present were also less likely to produce MHR. MHR correlated closely with cycloplegic refraction (r = 0.93, mean difference 0.07 D, p = n.s., 95% confidence interval +/-<0.25 D) after correction by a calibration factor. Conclusions. Maximum relaxation of accommodation occurred for binocular targets receding into the distance. Proximal and disparity cues aid relaxation of accommodation to a greater extent than blur, and thus non-cycloplegic refraction targets should incorporate these cues. This is especially important in screening contexts with a brief opportunity to test for significant hyperopia. MHR in our laboratory was found to be a reliable estimation of cycloplegic refraction. (Optom Vis Sci 2009;86:1276-1286)

High signal to noise ratio THz spectroscopy with ASOPS and signal processing schemes for mapping and controlling molecular and bulk relaxation processes

Asynchronous Optical Sampling has the potential to improve signal to noise ratio in THz transient sperctrometry. The design of an inexpensive control scheme for synchronising two femtosecond pulse frequency comb generators at an offset frequency of 20 kHz is discussed. The suitability of a range of signal processing schemes adopted from the Systems Identification and Control Theory community for further processing recorded THz transients in the time and frequency domain are outlined. Finally, possibilities for femtosecond pulse shaping using genetic algorithms are mentioned.