Vibrational perturbation theory

Expressions are derived for the Jacobian of the coriolis ζ interaction constants and the centrifugal stretching constants (DJ, DJK, etc.) with respect to the force constants in a vibrating-rotating molecule.

The domain derivative in rough-surface scattering and rigorous estimates for first-order perturbation theory

We investigate Fréchet differentiability of the scattered field with respect to variation in the boundary in the case of time–harmonic acoustic scattering by an unbounded, sound–soft, one–dimensional rough surface. We rigorously prove the differentiability of the scattered field and derive a characterization of the Fréchet derivative as the solution to a Dirichlet boundary value problem. As an application of these results we give rigorous error estimates for first–order perturbation theory, justifying small perturbation methods that have a long history in the engineering literature. As an application of our rigorous estimates we show that a plane acoustic wave incident on a sound–soft rough surface can produce an unbounded scattered field.

Vibrational intensities in methane

The absorption intensities of the two infra-red active vibrations in methane have been obtained from a perturbation calculation on the equilibrium wave functions derived in the preceding paper. The perturbation field is the change in the potential field due to the nuclei which results from moving the nuclei in the vibrational coordinate concerned, and a simplified form of second order perturbation theory, developed by Pople and Schofield, is used for the calculation. The main approximation involved is the neglect of f and higher harmonics in the spherical harmonic expansion of the nuclear field. The resulting dipole moment derivatives are approximately three times larger than the experimental values, but they show qualitative features and sign relationships which are significant.

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O-2. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.08 +/- 0.04) + (1.57 +/- 0.32 kJ mol(-1))/RT ln10 The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H2SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O + SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T -> S process in H2SiOO. This process has a small spin orbit coupling matrix element, consistent with an estimate of its rate constant of 1 x 10(9) s(-1) obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O-2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2 + O-2 and SiCl2 + O-2.

Gas phase kinetic and quantum chemical studies of the reactions of silylene with the methylsilanes. Absolute rate constants, temperature dependences, RRKM modelling and potential energy surfaces

Time resolved studies of silylene, SiH2, generated by the 193 nm laser. ash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3 - 100 Torr with SF6 as bath gas and at five temperatures in the range 300 - 625 K. Only slight pressure dependences were found for SiH2 + MeSiH3 ( 485 and 602 K) and for SiH2 + Me2SiH2 ( 600 K). The high pressure rate constants gave the following Arrhenius parameters: [GRAPHICS] These are consistent with fast, near to collision-controlled, association processes. RRKM modelling calculations are consistent with the observed pressure dependences ( and also the lack of them for SiH2 + Me3SiH). Ab initio calculations at both second order perturbation theory (MP2) and coupled cluster (CCSD(T)) levels, showed the presence of weakly-bound complexes along the reaction pathways. In the case of SiH2 + MeSiH3 two complexes, with different geometries, were obtained consistent with earlier studies of SiH2 + SiH4. These complexes were stabilised by methyl substitution in the substrate silane, but all had exceedingly low barriers to rearrangement to product disilanes. Although methyl groups in the substrate silane enhance the intrinsic SiH2 insertion rates, it is doubtful whether the intermediate complexes have a significant effect on the kinetics. A further calculation on the reaction MeSiH + SiH4 shows that the methyl substitution in the silylene should have a much more significant kinetic effect ( as observed in other studies).

Finite departure from convective quasi-equilibrium: periodic cycle and discharge-recharge mechanism

A simple self–contained theory is proposed for describing life cycles of convective systems as a discharge–recharge process. A closed description is derived for the dynamics of an ensemble of convective plumes based on an energy cycle. The system consists of prognostic equations for the cloud work function and the convective kinetic energy. The system can be closed by intro ducing a functional relationship between the convective kinetic energy and the cloud–base mass flux. The behaviour of this system is considered under a bulk simplification. Previous cloud–resolving mo delling as well as bulk statistical theories for ensemble convective systems suggest that a plausible relationship would be to assume that the convective kinetic energy is linearly proportional to the cloud–base mass flux. As a result, the system reduces to a nonlinear dynamical system with two dependent variables, the cloud–base mass flux and the cloud work function. The fully nonlinear solution of this system always represents a periodic cycle regardless of the initial condition under constant large–scale forcing. Importantly, the inclusion of energy dissipation in this model does not in itself lead the system to an equilibrium.

Spectral asymmetry of the massless Dirac operator on a 3-torus

Consider the massless Dirac operator on a 3-torus equipped with Euclidean metric and standard spin structure. It is known that the eigenvalues can be calculated explicitly: the spectrum is symmetric about zero and zero itself is a double eigenvalue. The aim of the paper is to develop a perturbation theory for the eigenvalue with smallest modulus with respect to perturbations of the metric. Here the application of perturbation techniques is hindered by the fact that eigenvalues of the massless Dirac operator have even multiplicity, which is a consequence of this operator commuting with the antilinear operator of charge conjugation (a peculiar feature of dimension 3). We derive an asymptotic formula for the eigenvalue with smallest modulus for arbitrary perturbations of the metric and present two particular families of Riemannian metrics for which the eigenvalue with smallest modulus can be evaluated explicitly. We also establish a relation between our asymptotic formula and the eta invariant.

Gas-phase rate coefficients for the reactions of O(3P), S(3P), Se(3P), and Te(3P) with alkenes: application of perturbation frontier molecular orbital theory, correlations, and structure-activity relations (SARs)

The kinetics of the reactions of the atoms O(P-3), S(P-3), Se(P-3), and Te((3)p) with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. These correlations may be employed to predict rate coefficients from the calculated HOMO energy of any other alkene of interest. The rate coefficients obtained from the correlations were used to formulate structure-activity relations (SARs) for reactions of O((3)p), S(P-3), Se (P-3), and Te((3)p) with alkenes. A comparison of the values predicted by both the correlations and the SARs with experimental data where they exist allowed us to assess the reliability of our method. We demonstrate the applicability of perturbation frontier molecular orbital theory to gas-phase reactions of these atoms with alkenes. The correlations are apparently not applicable to reactions of C(P-3), Si(P-3), N(S-4), and Al(P-2) atoms with alkenes, a conclusion that could be explained in terms of a different mechanism for reaction of these atoms.

A simple analysis of thermodynamic properties for classical plasmas: I. theory

By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

Determination of tube theory parameters using a simple grid model as an example

Although the tube theory is successful in describing entangled polymers qualitatively, a more quantitative description requires precise and consistent definitions of its parameters. Here we investigate the simplest model of entangled polymers, namely a single Rouse chain in a cubic lattice of line obstacles, and illustrate the typical problems and uncertainties of the tube theory. In particular we show that in general one needs 3 entanglement related parameters, but only 2 combinations of them are relevant for the long-time dynamics. Conversely, the plateau modulus can not be determined from these two parameters and requires a more detailed model of entanglements with explicit entanglement forces, such as the slipsprings model. It is shown that for the grid model the Rouse time within the tube is larger than the Rouse time of the free chain, in contrast to what the standard tube theory assumes.

Model-measurement comparison of mesospheric temperature inversions, and a simple theory for their occurrence

Mesospheric temperature inversions are well established observed phenomena, yet their properties remain the subject of ongoing research. Comparisons between Rayleigh-scatter lidar temperature measurements obtained by the University of Western Ontario's Purple Crow Lidar (42.9°N, 81.4°W) and the Canadian Middle Atmosphere Model are used to quantify the statistics of inversions. In both model and measurements, inversions occur most frequently in the winter and exhibit an average amplitude of ∼10 K. The model exhibits virtually no inversions in the summer, while the measurements show a strongly reduced frequency of occurrence with an amplitude about half that in the winter. A simple theory of mesospheric inversions based on wave saturation is developed, with no adjustable parameters. It predicts that the environmental lapse rate must be less than half the adiabatic lapse rate for an inversion to form, and it predicts the ratio of the inversion amplitude and thickness as a function of environmental lapse rate. Comparison of this prediction to the actual amplitude/thickness ratio using the lidar measurements shows good agreement between theory and measurements.

An interpretation of baroclinic initial value problems: results for simple basic states with nonzero interior PV gradients

In the Eady model, where the meridional potential vorticity (PV) gradient is zero, perturbation energy growth can be partitioned cleanly into three mechanisms: (i) shear instability, (ii) resonance, and (iii) the Orr mechanism. Shear instability involves two-way interaction between Rossby edge waves on the ground and lid, resonance occurs as interior PV anomalies excite the edge waves, and the Orr mechanism involves only interior PV anomalies. These mechanisms have distinct implications for the structural and temporal linear evolution of perturbations. Here, a new framework is developed in which the same mechanisms can be distinguished for growth on basic states with nonzero interior PV gradients. It is further shown that the evolution from quite general initial conditions can be accurately described (peak error in perturbation total energy typically less than 10%) by a reduced system that involves only three Rossby wave components. Two of these are counterpropagating Rossby waves—that is, generalizations of the Rossby edge waves when the interior PV gradient is nonzero—whereas the other component depends on the structure of the initial condition and its PV is advected passively with the shear flow. In the cases considered, the three-component model outperforms approximate solutions based on truncating a modal or singular vector basis.

Making development simple. The genetic deterministic hypothesis for economic development

This paper discusses the dangers inherent in allempting to simplify something as complex as development. It does this by exploring the Lynn and Vanhanen theory of deterministic development which asserts that varying levels of economic development seen between countries can be explained by differences in 'national intelligence' (national IQ). Assuming that intelligence is genetically determined, and as different races have been shown to have different IQ, then they argue that economic development (measured as GDP/capita) is largely a function of race and interventions to address imbalances can only have a limited impact. The paper presents the Lynne and Vanhanen case and critically discusses the data and analyses (linear regression) upon which it is based. It also extends the cause-effect basis of Lynne and Vanhanen's theory for economic development into human development by using the Human Development Index (HDI). It is argued that while there is nothing mathematically incorrect with their calculations, there are concerns over the data they employ. Even more fundamentally it is argued that statistically significant correlations between the various components of the HDI and national IQ can occur via a host of cause-effect pathways, and hence the genetic determinism theory is far from proven. The paper ends by discussing the dangers involved in the use of over-simplistic measures of development as a means of exploring cause-effect relationships. While the creators of development indices such as the HDI have good intentions, simplistic indices can encourage simplistic explanations of under-development. (c) 2005 Elsevier B.V. All rights reserved.

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.

A simple theoretical model for the intensification of tropical cyclones and polar lows

A simple theoretical model for the intensification of tropical cyclones and polar lows is developed using a minimal set of physical assumptions. These disturbances are assumed to be balanced systems intensifying through the WISHE (Wind-Induced Surface Heat Exchange) intensification mechanism, driven by surface fluxes of heat and moisture into an atmosphere which is neutral to moist convection. The equation set is linearized about a resting basic state and solved as an initial-value problem. A system is predicted to intensify with an exponential perturbation growth rate scaled by the radial gradient of an efficiency parameter which crudely represents the effects of unsaturated processes. The form of this efficiency parameter is assumed to be defined by initial conditions, dependent on the nature of a pre-existing vortex required to precondition the atmosphere to a state in which the vortex can intensify. Evaluation of the simple model using a primitive-equation, nonlinear numerical model provides support for the prediction of exponential perturbation growth. Good agreement is found between the simple and numerical models for the sensitivities of the measured growth rate to various parameters, including surface roughness, the rate of transfer of heat and moisture from the ocean surface, and the scale for the growing vortex.