The calculation of force constants and normal co-ordinates II: methyl fluoride

The mathematical difficulties which can arise in the force constant refinement procedure for calculating force constants and normal co-ordinates are described and discussed. The method has been applied to the methyl fluoride molecule, using an electronic computer. The best values of the twelve force constants in the most general harmonic potential field were obtained to fit twenty-two independently observed experimental data, these being the six vibration frequencies, three Coriolis zeta constants and two centrifugal stretching constants DJ and DJK, for both CH3F and CD3F. The calculations have been repeated both with and without anharmonicity corrections to the vibration frequencies. All the experimental data were weighted according to the reliability of the observations, and the corresponding standard errors and correlation coefficients of the force constants have been deduced. The final force constants are discussed briefly, and compared with previous treatments, particularly with a recent Urey-Bradley treatment for this molecule.

The calculation of force constants and normal coordinates III: constrained force fields for the methyl halides

A method is discussed for imposing any desired constraint on the force field obtained in a force constant refinement calculation. The application of this method to force constant refinement calculations for the methyl halide molecules is reported. All available data on the vibration frequencies, Coriolis interaction constants and centrifugal stretching constants of CH3X and CD3X molecules were used in the refinements, but despite this apparent abundance of data it was found that constraints were necessary in order to obtain a unique solution to the force field. The results of unconstrained calculations, and of three different constrained calculations, are reported in this paper. The constrained models reported are a Urey—Bradley force field, a modified valence force field, and a constraint based on orbital-following bond-hybridization arguments developed in the following paper. The results are discussed, and compared with previous results for these molecules. The third of the above models is found to reproduce the observed data better than either of the first two, and additional reasons are given for preferring this solution to the force field for the methyl halide molecules.

Vibration-rotation spectra and the harmonic force field of HOCl

Vibration-rotation spectra of HOCl have been measured at a resolution of 0.05 cm−1 to determine vibration rotation constants, and 35–37 Cl isotope shifts in the vibration frequencies. The spectrum of DOCl has also been recorded, and a preliminary analysis for the band origins has been made. The vibrational frequency data and centrifugal distortion constants have been used to determine the harmonic force field in a least-squares refinement; the force field obtained also gives a good fit to data on the vibrational contributions to the inertial defect. The equilibrium rotational constants of HOCl have been obtained, and an equilibrium structure has been estimated.

Nitrous acid: vibrational frequency shifts due to 15N substitution, and the harmonic force field

Vibration rotation spectra of HO15 NO and DO15 NO have been measured at a resolution of 0•04 cm-1 to determine the isotopic shifts in the vibrational band origins. These have been used together with recently determined data on the vibrational band origins, Coriolis constants, and centrifugal distorition constants, to determine the harmonic force field of both cis and trans nitrous acid in least squares refinement calculations. The results are discussed in relation to recent ab initio calculations, the inertia defects, and the torsional potential function.

The harmonic force field and rz structure of HNCO

The presently available microwave, millimeter wave, and far-infrared data of five isotopic species of isocyanic acid, namely, HNCO, H15NCO, HN13CO, HNC18O, and DNCO, have been used to obtain improved values of the ground-state rotational constants, the five quartic distortion constants, and some higher-order distortion constants in the Ir S reduced Hamiltonian of Watson. The appropriate planarity relation among the quartic centrifugal distortion constants has been imposed in the fitting procedure. The general harmonic force field of isocyanic acid has been determined using all existing data, and assuming a trans bent equilibrium geometry of the molecule with an NCO angle of 170°. Finally an rz structure has been obtained using the Az, Bz, and Cz rotational constants of five isotopic species. The bending of the NCO chain is found to be 8° in the trans configuration.

ASYM20: a program for force constant and normal coordinate calculations, with a critical review of the theory involved

The theory of harmonic force constant refinement calculations is reviewed, and a general-purpose program for force constant and normal coordinate calculations is described. The program, called ASYM20. is available through Quantum Chemistry Program Exchange. It will work on molecules of any symmetry containing up to 20 atoms and will produce results on a series of isotopomers as desired. The vibrational secular equations are solved in either nonredundant valence internal coordinates or symmetry coordinates. As well as calculating the (harmonic) vibrational wavenumbers and normal coordinates, the program will calculate centrifugal distortion constants, Coriolis zeta constants, harmonic contributions to the α′s. root-mean-square amplitudes of vibration, and other quantities related to gas electron-diffraction studies and thermodynamic properties. The program will work in either a predict mode, in which it calculates results from an input force field, or in a refine mode, in which it refines an input force field by least squares to fit observed data on the quantities mentioned above. Predicate values of the force constants may be included in the data set for a least-squares refinement. The program is written in FORTRAN for use on a PC or a mainframe computer. Operation is mainly controlled by steering indices in the input data file, but some interactive control is also implemented.

The general harmonic force field of methyl fluoride

The complete general harmonic force field of methyl flouride was recalculated using the most recent literature frequency, Coriolis ζ, and centrifugal distortion data for 12CH3F, 13CH3F, 12CD3F, 12CHD2F and 12CH2DF. The anharmonic corrections applied to the observed frequency data and the adopted molecular geometry are considered to be more realistic than those used hitherto. There is excellent overall agreement between the fitted force constants and the highest quality ab initio force field currently available.

Magnetic drive system for a new centrifugal rotary blood pump

The purpose of this investigation was to design a novel magnetic drive and bearing system for a new centrifugal rotary blood pump (CRBP). The drive system consists of two components: (i) permanent magnets within the impeller of the CRBP; and (ii) the driving electromagnets. Orientation of the magnets varies from axial through to 60° included out-lean (conical configuration). Permanent magnets replace the electromagnet drive to allow easier characterization. The performance characteristics tested were the axial force of attraction between the stator and rotor at angles of rotational alignment, Ø, and the corresponding torque at those angles. The drive components were tested for various magnetic cone angles, ?. The test was repeated for three backing conditions: (i) non-backed; (ii) steel-cupped; and (iii) steel plate back-iron, performed on an Instron tensile testing machine. Experimental results were expanded upon through finite element and boundary element analysis (BEM). The force/torque characteristics were maximal for a 12-magnet configuration at 0° cone angle with steel-back iron (axial force = 60 N, torque = 0.375 Nm). BEM showed how introducing a cone angle increases the radial restoring force threefold while not compromising axial bearing force. Magnets in the drive system may be orientated not only to provide adequate coupling to drive the CRBP, but to provide significant axial and radial bearing forces capable of withstanding over 100 m/s2 shock excitation on the impeller. Although the 12 magnet 0° (?) configuration yielded the greatest force/torque characteristic, this was seen as potentially unattractive as this magnetic cone angle yielded poor radial restoring force characteristics.

Relationship Between Orofacial Function, Dentofacial Morphology, And Bite Force In Young Subjects.

The aim was to evaluate the relationship between orofacial function, dentofacial morphology, and bite force in young subjects. Three hundred and sixteen subjects were divided according to dentition stage (early, intermediate, and late mixed and permanent dentition). Orofacial function was screened using the Nordic Orofacial Test-Screening (NOT-S). Orthodontic treatment need, bite force, lateral and frontal craniofacial dimensions and presence of sleep bruxism were also assessed. The results were submitted to descriptive statistics, normality and correlation tests, analysis of variance, and multiple linear regression to test the relationship between NOT-S scores and the studied independent variables. The variance of NOT-S scores between groups was not significant. The evaluation of the variables that significantly contributed to NOT-S scores variation showed that age and presence of bruxism related to higher NOT-S total scores, while the increase in overbite measurement and presence of closed lip posture related to lower scores. Bite force did not show a significant relationship with scores of orofacial dysfunction. No significant correlations between craniofacial dimensions and NOT-S scores were observed. Age and sleep bruxism were related to higher NOT-S scores, while the increase in overbite measurement and closed lip posture contributed to lower scores of orofacial dysfunction.

Bipolar Tribocharging Signal During Friction Force Fluctuations At Metal-insulator Interfaces.

Friction and triboelectrification of materials show a strong correlation during sliding contacts. Friction force fluctuations are always accompanied by two tribocharging events at metal-insulator [e.g., polytetrafluoroethylene (PTFE)] interfaces: injection of charged species from the metal into PTFE followed by the flow of charges from PTFE to the metal surface. Adhesion maps that were obtained by atomic force microscopy (AFM) show that the region of contact increases the pull-off force from 10 to 150 nN, reflecting on a resilient electrostatic adhesion between PTFE and the metallic surface. The reported results suggest that friction and triboelectrification have a common origin that must be associated with the occurrence of strong electrostatic interactions at the interface.

Retention force of T-bar clasps for titanium and cobalt-chromium removable partial dentures

The objective of this study was to evaluate the retention force of T-bar clasps made from commercially pure titanium (CP Ti) and cobalt-chromium (Co-Cr) alloy by the insertion/removal test simulating 5 years use. Thirty-six frameworks were cast from CP Ti (n=18) and Co-Cr alloy (n=18) with identical prefabricated patterns on refractory casts from a distal extension mandibular hemi-arch segment. The castings were made on a vacuum-pressure machine, under vacuum and argon atmosphere. Each group was subdivided in three, corresponding to 0.25 mm, 0.50 mm and 0.75 mm undercuts, respectively. No polishing procedures were performed to ensure uniformity. The specimens were subjected to an insertion/removal test and data was analyzed statistically to compare CP Ti and Co-Cr alloy in the same undercut (Student's t-test for independent samples) and each material in different undercuts (one-way ANOVA) (p=0.05). Comparisons between materials revealed significant differences (p=0.017) only for the 0.50-mm undercut. No significant differences (p>0.05) were found when comparing the same material for the undercuts. It may be concluded that for different undercuts, both Co-Cr alloy and CP Ti had no significant differences for T-bar clasps; CP Ti showed the lowest retention force values when compared to Co-Cr alloy in each undercut, but with significant difference only for the 0.50-mm undercut; and both materials maintained the retentive capacity during the simulation test.

Bite force in temporomandibular dysfunction (TMD) and healthy complete denture wearers

The signs and symptoms of temporomandibular dysfunction (TMD) may contribute to reduce bite force and muscular activity. The aims of this study were to compare bite force in complete denture wearers with TMD (TMD group) and without TMD (healthy group).The TMD group consisted of 9 individuals, who had worn a maxillary and a mandibular complete removable denture for more than 10 years. The healthy group consisted of 9 participants who wore dentures and had satisfactory interocclusal and maxillomandibular relationship. Helkimo Index was used to analyze the dysfunction level. Maximum bite force was measured using a digital dynamometer with capacity of 100 kgf and adapted to oral conditions.The TMD group presented smaller mean bite force values than the healthy group, though without statistical significance (p>0.05). This outcome suggests that the TMD signs and symptoms and the structural conditions of the dentures did not affect the maximal bite force of complete denture wearers.

Do synergies improve accuracy? A study of speed-accuracy trade-offs during finger force production

We explored possible effects of negative covariation among finger forces in multifinger accurate force production tasks on the classical Fitts's speed-accuracy trade-off. Healthy subjects performed cyclic force changes between pairs of targets ""as quickly and accurately as possible."" Tasks with two force amplitudes and six ratics of force amplitude to target size were performed by each of the four fingers of the right hand and four finger combinations. There was a close to linear relation between movement time and the log-transformed ratio of target amplitude to target size across all finger combinations. There was a close to linear relation between standard deviation of force amplitude and movement time. There were no differences between the performance of either of the two ""radial"" fingers (index and middle) and the multifinger tasks. The ""ulnar"" fingers (little and ring) showed higher indices of variability and longer movement times as compared with both ""radial"" fingers and multifinger combinations. We conclude that potential effects of the negative covariation and also of the task-sharing across a set of fingers are counterbalanced by an increase in individual finger force variability in multifinger tasks as compared with single-finger tasks. The results speak in favor of a feed-forward model of multifinger synergies. They corroborate a hypothesis that multifinger synergies are created not to improve overall accuracy, but to allow the system larger flexibility, for example to deal with unexpected perturbations and concomitant tasks.

Tooth Movement Activates the Central Amygdala and the Lateral Hypothalamus by the Magnitude of the Force Applied

Objective: To determine if the magnitude of the force used to induce incisor tooth movement promotes distinct activation in cells in the central amygdala (CEA) and lateral hypothalamus (LH) of rats. Also, the effect of morphine on Fos immunoreactivity (Fos-IR) was investigated in these nuclei. Materials and Methods: Adult male rats were anesthetized and divided into six groups: only anesthetized (control), without orthodontic appliance (OA), OA but without force, OA activated with 30g or 70g, OA with 70g in animals pretreated with morphine (2 mg/kg, intraperitoneal). Three hours after the onset of the experiment the rats were reanesthetized and perfused with 4% paraformaldehyde. The brains were removed and fixed, and sections containing CEA and LH were processed for Fos protein immunohistochemistry. Results: The results show that in the control group, the intramuscular injection of a ketamine/xylazine mixture did not induce Fos-IR cells in the CEA or in the LH. Again, the without force group showed a little Fos-IR. However, in the 70g group the Fos-IR was the biggest observed (P < .05, Tukey) in the CEA and LH compared with the other groups. In the 30g group, the Fos-IR did not differ from the control group, the without OA group, and the without force group. Furthermore, pretreatment with morphine in the 70g group reduced Fos-IR in these regions. Conclusions: Tooth movement promotes Fos-IR in the CEA and LH according to the magnitude of the force applied. (Angle Orthod. 2010;80:111-115.)

Relationship Between Surface Topography and Energy Density Distribution of Er,Cr:YSGG Beam on Irradiated Dentin: An Atomic Force Microscopy Study

Objective: The aim of this study was to assess by atomic force microscopy (AFM) the effect of Er,Cr:YSGG laser application on the surface microtopography of radicular dentin. Background: Lasers have been used for various purposes in dentistry, where they are clinically effective when used in an appropriate manner. The Er, Cr: YSGG laser can be used for caries prevention when settings are below the ablation threshold. Materials and Methods: Four specimens of bovine dentin were irradiated using an Er, Cr:YSGG laser (lambda = 2.78 mu m), at a repetition rate of 20 Hz, with a 750-mu m-diameter sapphire tip and energy density of 2.8 J/cm(2) (12.5 mJ/pulse). After irradiation, surface topography was analyzed by AFM using a Si probe in tapping mode. Quantitative and qualitative information concerning the arithmetic average roughness (Ra) and power spectral density analyses were obtained from central, intermediate, and peripheral areas of laser pulses and compared with data from nonirradiated samples. Results: Dentin Ra for different areas were as follows: central, 261.26 (+/- 21.65) nm; intermediate, 83.48 (+/- 6.34) nm; peripheral, 45.8 (+/- 13.47) nm; and nonirradiated, 35.18 (+/- 2.9) nm. The central region of laser pulses presented higher ablation of intertubular dentin, with about 340-760 nm height, while intermediate, peripheral, and nonirradiated regions presented no difference in height of peritubular and interperitubular dentin. Conclusion: According to these results, we can assume that even when used at a low-energy density parameter, Er, Cr: YSGG laser can significantly alter the microtopography of radicular dentin, which is an important characteristic to be considered when laser is used for clinical applications.