The calculation of accurate normal coordinates I: general theory, and application to methane

The calculation of accurate and reliable vibrational potential functions and normal co-ordinates is discussed, for such simple polyatomic molecules as it may be possible. Such calculations should be corrected for the effects of anharmonicity and of resonance interactions between the vibrational states, and should be fitted to all the available information on all isotopic species: particularly the vibrational frequencies, Coriolis zeta constants and centrifugal distortion constants. The difficulties of making these corrections, and of making use of the observed data are reviewed. A programme for the Ferranti Mercury Computer is described by means of which harmonic vibration frequencies and normal co-ordinate vectors, zeta factors and centrifugal distortion constants can be calculated, from a given force field and from given G-matrix elements, etc. The programme has been used on up to 5 × 5 secular equations for which a single calculation and output of results takes approximately l min; it can readily be extended to larger determinants. The best methods of using such a programme and the possibility of reversing the direction of calculation are discussed. The methods are applied to calculating the best possible vibrational potential function for the methane molecule, making use of all the observed data.

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 use of bootstrapped Malmquist indices to reassess productivity change findings: an application to a sample of Polish farms

This article assesses the extent to which sampling variation affects findings about Malmquist productivity change derived using data envelopment analysis (DEA), in the first stage by calculating productivity indices and in the second stage by investigating the farm-specific change in productivity. Confidence intervals for Malmquist indices are constructed using Simar and Wilson's (1999) bootstrapping procedure. The main contribution of this article is to account in the second stage for the information in the second stage provided by the first-stage bootstrap. The DEA SEs of the Malmquist indices given by bootstrapping are employed in an innovative heteroscedastic panel regression, using a maximum likelihood procedure. The application is to a sample of 250 Polish farms over the period 1996 to 2000. The confidence intervals' results suggest that the second half of 1990s for Polish farms was characterized not so much by productivity regress but rather by stagnation. As for the determinants of farm productivity change, we find that the integration of the DEA SEs in the second-stage regression is significant in explaining a proportion of the variance in the error term. Although our heteroscedastic regression results differ with those from the standard OLS, in terms of significance and sign, they are consistent with theory and previous research.

Large vibrational variational calculations using 'multimode' and an iterative diagonalization technique

We have favoured the variational (secular equation) method for the determination of the (ro-) vibrational energy levels of polyatomic molecules. We use predominantly the Watson Hamiltonian in normal coordinates and an associated given potential in the variational code 'Multimode'. The dominant cost is the construction and diagonalization of matrices of ever-increasing size. Here we address this problem, using pertubation theory to select dominant expansion terms within the Davidson-Liu iterative diagonalization method. Our chosen example is the twelve-mode molecule methanol, for which we have an ab initio representation of the potential which includes the internal rotational motion of the OH group relative to CH3. Our new algorithm allows us to obtain converged energy levels for matrices of dimensions in excess of 100 000.

A reaction surface Hamiltonian study of malonaldehyde

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms. The vibrational energy levels are evaluated by solving the variational secular equations, using a basis of products of Hermite polynomials and appropriate functions of s(1),s(2). Our selected example is malonaldehyde (N=9) and we choose as surface parameters two OH distances of the migrating H in the internal hydrogen transfer. The reaction surface Hamiltonian is ideally suited to the study of the kind of tunneling dynamics present in malonaldehyde. Our results are in good agreement with previous calculations of the zero point tunneling splitting and in general agreement with observed data. Interpretation of our two-dimensional reaction surface states suggests that the OH stretching fundamental is incorrectly assigned in the infrared spectrum. This mode appears at a much lower frequency in our calculations due to substantial transition state character. (c) 2006 American Institute of Physics.

Numerical study of 2D heat transfer in a scraped surface heat exchanger

A numerical study of fluid mechanics and heat transfer in a scraped surface heat exchanger with non-Newtonian power law fluids is undertaken. Numerical results are generated for 2D steady-state conditions using finite element methods. The effect of blade design and material properties, and especially the independent effects of shear thinning and heat thinning on the flow and heat transfer, are studied. The results show that the gaps at the root of the blades, where the blades are connected to the inner cylinder, remove the stagnation points, reduce the net force on the blades and shift the location of the central stagnation point. The shear thinning property of the fluid reduces the local viscous dissipation close to the singularity corners, i.e. near the tip of the blades, and as a result the local fluid temperature is regulated. The heat thinning effect is greatest for Newtonian fluids where the viscous dissipation and the local temperature are highest at the tip of the blades. Where comparison is possible, very good agreement is found between the numerical results and the available data. Aspects of scraped surface heat exchanger design are assessed in the light of the results. (C) 2003 Elsevier Ltd. All rights reserved.

Religious schools, social values, and economic attitudes: evidence from Bangladesh

This paper uses new data on female graduates of registered secondary secular schools and madrasas from rural Bangladesh and tests whether there exist attitudinal gaps by school type and what teacher-specific factors explain these gaps. Even after controlling for a rich set of individual, family and school traits, we find that madrasa graduates differ on attitudes associated with issues such as working mothers, desired fertility, and higher education for girls, when compared to their secular schooled peers. On the other hand, madrasa education is associated with attitudes that are still conducive to democracy. We also find that exposure to female and younger teacher is associated with more favorable attitudes among graduates.

Facebook faith - social networking in a faith based community

This paper views the increasing social networking as an efficient emerging ministry to the moveable generation. Through social network such as Facebook, ministry from a pastoral perspective can become more authentic and meaningful. Ministry is relational. Social Networking sites provide a strong platform to being part in other people’s life. Social networking and living online builds community beyond geographical boarders. Young adults and youths digital identity often reflects their faith, this is supported by research which suggests a practice of more openness to share and expose private issues online. Spiritual and religious views are freely shared, creating sacred spaces in the midst of life practising a holistic faith identity in a secular community. Providing a strong platform for information flow, Social Network is attractive in a postmodern society where inviting people to join in events are perceived as non threatening, making church community events transparent and available to people who do not attend church, inviting spiritual friendships and relationships. Social Networking strengthens relationship in a non hierarchical manner and invites the minister into lives where there previously would have been barriers, engaging in prayer and bible study as well as pastoral care through social networking, thus relationships deepens via social networking making people real. It has been observed that, although community building happens on the net, church affiliation loyalty remains to the local community. Therefore presence ministry though social networks emerges as a core form of ministry, where relations to youth who move from local church to university campuses are kept alive. The asynchronous nature of communication within social networking eases the minister in her work. The minister is able to engage with many individuals at the same time. Before the minister could visit one person at a time, now she visits 5-6 individuals at any given time. Therefore social networking not only increases the quality of the work, but also empowers the minister to be more efficient.

On the existence of extreme waves and the Stokes conjecture with vorticity

This is a study of singular solutions of the problem of traveling gravity water waves on flows with vorticity. We show that, for a certain class of vorticity functions, a sequence of regular waves converges to an extreme wave with stagnation points at its crests. We also show that, for any vorticity function, the profile of an extreme wave must have either a corner of 120° or a horizontal tangent at any stagnation point about which it is supposed symmetric. Moreover, the profile necessarily has a corner of 120° if the vorticity is nonnegative near the free surface.

Steady periodic water waves with constant vorticity: regularity and local bifurcation

This paper studies periodic traveling gravity waves at the free surface of water in a flow of constant vorticity over a flat bed. Using conformal mappings the free-boundary problem is transformed into a quasilinear pseudodifferential equation for a periodic function of one variable. The new formulation leads to a regularity result and, by use of bifurcation theory, to the existence of waves of small amplitude even in the presence of stagnation points in the flow.

L’amant tenu par la bride : Itinéraires d'un motif courtois chez Gaucelm Faidit et sur un coffret limousin

A comparison between selected lyrics and iconography of the late twelfth-century troubadour Gaucelm Faidit and a 'courtly love' image on a secular casket of Limoges enamel produced in the same period.

PINCER trial: a cluster randomised trial comparing the effectiveness and cost-effectiveness of a pharmacist-led IT-based intervention with simple feedback in reducing rates of clinically important errors in medicines management in general practices

Background: Medication errors in general practice are an important source of potentially preventable morbidity and mortality. Building on previous descriptive, qualitative and pilot work, we sought to investigate the effectiveness, cost-effectiveness and likely generalisability of a complex pharm acist-led IT-based intervention aiming to improve prescribing safety in general practice. Objectives: We sought to: • Test the hypothesis that a pharmacist-led IT-based complex intervention using educational outreach and practical support is more effective than simple feedback in reducing the proportion of patients at risk from errors in prescribing and medicines management in general practice. • Conduct an economic evaluation of the cost per error avoided, from the perspective of the National Health Service (NHS). • Analyse data recorded by pharmacists, summarising the proportions of patients judged to be at clinical risk, the actions recommended by pharmacists, and actions completed in the practices. • Explore the views and experiences of healthcare professionals and NHS managers concerning the intervention; investigate potential explanations for the observed effects, and inform decisions on the future roll-out of the pharmacist-led intervention • Examine secular trends in the outcome measures of interest allowing for informal comparison between trial practices and practices that did not participate in the trial contributing to the QRESEARCH database. Methods Two-arm cluster randomised controlled trial of 72 English general practices with embedded economic analysis and longitudinal descriptive and qualitative analysis. Informal comparison of the trial findings with a national descriptive study investigating secular trends undertaken using data from practices contributing to the QRESEARCH database. The main outcomes of interest were prescribing errors and medication monitoring errors at six- and 12-months following the intervention. Results: Participants in the pharmacist intervention arm practices were significantly less likely to have been prescribed a non-selective NSAID without a proton pump inhibitor (PPI) if they had a history of peptic ulcer (OR 0.58, 95%CI 0.38, 0.89), to have been prescribed a beta-blocker if they had asthma (OR 0.73, 95% CI 0.58, 0.91) or (in those aged 75 years and older) to have been prescribed an ACE inhibitor or diuretic without a measurement of urea and electrolytes in the last 15 months (OR 0.51, 95% CI 0.34, 0.78). The economic analysis suggests that the PINCER pharmacist intervention has 95% probability of being cost effective if the decision-maker’s ceiling willingness to pay reaches £75 (6 months) or £85 (12 months) per error avoided. The intervention addressed an issue that was important to professionals and their teams and was delivered in a way that was acceptable to practices with minimum disruption of normal work processes. Comparison of the trial findings with changes seen in QRESEARCH practices indicated that any reductions achieved in the simple feedback arm were likely, in the main, to have been related to secular trends rather than the intervention. Conclusions Compared with simple feedback, the pharmacist-led intervention resulted in reductions in proportions of patients at risk of prescribing and monitoring errors for the primary outcome measures and the composite secondary outcome measures at six-months and (with the exception of the NSAID/peptic ulcer outcome measure) 12-months post-intervention. The intervention is acceptable to pharmacists and practices, and is likely to be seen as costeffective by decision makers.

Scripture, style and persuasion in seventeenth-century English theories of preaching

The distinction between a Puritan ‘plain’ and a Laudian ‘metaphysical’ preaching style rests on secular rhetorical theories of persuasion that are relatively unimportant to early Stuart homiletics but are central to later Latitudinarian polemics on preaching. Instead, the ‘English Reformed’ theory and method of sermon composition rests on the didactic function of preaching and the need for the Holy Spirit and hearers to co-operate with the preacher. Although Andrewes and some avant-garde conformists questioned this theory, they developed no alternative method of composition. Arguments made in the 1650s for direct inspiration by the Spirit contributed to the decline of both theory and method

Barbara Torelli Benedetti, Partenia, a pastoral play. A bilingual edition edited with notes and translation

This edition presents for the first time in print what is probably the earliest known secular, 'regular' play by a woman in Italy. As suggested in the introduction to the work, Torelli's play offers a fascinating example of female dramaturgy and creative adaptation of the pastoral genre in the context of late sixteenth-century Parma. Critical textual study is combined with new biographical material on the author and her literary milieu. The edition provides the first detailed palaeographical study of the complex Cremona manuscript of the play, which unusually includes emendations thought to be in the hand of the author herself (besides others). The transcription also describes for the first time in detail a newly discovered second manuscript of the play in Rome. The play-text is presented in the original Italian with a new facing English translation. Also included is the first transcription of the paratextual verse from the Cremona manuscript and the first transcribed collection of the author’s extant verse (both with translation).