Force constants and dipole moment derivatives of molecules from perturbed Hartree-Fock calculations II. Applications to limited basis set SCF-MO wavefunctions

The perturbed Hartree–Fock theory developed in the preceding paper is applied to LiH, BH, and HF, using limited basis‐set SCF–MO wavefunctions derived by previous workers. The calculated values for the force constant ke and the dipole‐moment derivative μ(1) are (experimental values in parentheses): LiH, ke  =  1.618(1.026)mdyn/Å,μ(1)  =  −18.77(−2.0±0.3)D/ÅBH,ke  =  5.199(3.032)mdyn/Å,μ(1)  =  −1.03(−)D/Å;HF,ke  =  12.90(9.651)mdyn/Å,μ(1)  =  −2.15(+1.50)D/Å. The values of the force on the proton were calculated exactly and according to the Hellmann–Feynman theorem in each case, and the discrepancies show that none of the wavefunctions used are close to the Hartree–Fock limit, so that the large errors in ke and μ(1) are not surprising. However no difficulties arose in the perturbed Hartree–Fock calculation, so that the application of the theory to more accurate wavefunctions appears quite feasible.

A statistical mechanical approach for the computation of the climatic response to general forcings

The climate belongs to the class of non-equilibrium forced and dissipative systems, for which most results of quasi-equilibrium statistical mechanics, including the fluctuation-dissipation theorem, do not apply. In this paper we show for the first time how the Ruelle linear response theory, developed for studying rigorously the impact of perturbations on general observables of non-equilibrium statistical mechanical systems, can be applied with great success to analyze the climatic response to general forcings. The crucial value of the Ruelle theory lies in the fact that it allows to compute the response of the system in terms of expectation values of explicit and computable functions of the phase space averaged over the invariant measure of the unperturbed state. We choose as test bed a classical version of the Lorenz 96 model, which, in spite of its simplicity, has a well-recognized prototypical value as it is a spatially extended one-dimensional model and presents the basic ingredients, such as dissipation, advection and the presence of an external forcing, of the actual atmosphere. We recapitulate the main aspects of the general response theory and propose some new general results. We then analyze the frequency dependence of the response of both local and global observables to perturbations having localized as well as global spatial patterns. We derive analytically several properties of the corresponding susceptibilities, such as asymptotic behavior, validity of Kramers-Kronig relations, and sum rules, whose main ingredient is the causality principle. We show that all the coefficients of the leading asymptotic expansions as well as the integral constraints can be written as linear function of parameters that describe the unperturbed properties of the system, such as its average energy. Some newly obtained empirical closure equations for such parameters allow to define such properties as an explicit function of the unperturbed forcing parameter alone for a general class of chaotic Lorenz 96 models. We then verify the theoretical predictions from the outputs of the simulations up to a high degree of precision. The theory is used to explain differences in the response of local and global observables, to define the intensive properties of the system, which do not depend on the spatial resolution of the Lorenz 96 model, and to generalize the concept of climate sensitivity to all time scales. We also show how to reconstruct the linear Green function, which maps perturbations of general time patterns into changes in the expectation value of the considered observable for finite as well as infinite time. Finally, we propose a simple yet general methodology to study general Climate Change problems on virtually any time scale by resorting to only well selected simulations, and by taking full advantage of ensemble methods. The specific case of globally averaged surface temperature response to a general pattern of change of the CO2 concentration is discussed. We believe that the proposed approach may constitute a mathematically rigorous and practically very effective way to approach the problem of climate sensitivity, climate prediction, and climate change from a radically new perspective.

Bayesian retrieval of complete posterior PDFs of oceanic rain rate from microwave observations

A new Bayesian algorithm for retrieving surface rain rate from Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) over the ocean is presented, along with validations against estimates from the TRMM Precipitation Radar (PR). The Bayesian approach offers a rigorous basis for optimally combining multichannel observations with prior knowledge. While other rain-rate algorithms have been published that are based at least partly on Bayesian reasoning, this is believed to be the first self-contained algorithm that fully exploits Bayes’s theorem to yield not just a single rain rate, but rather a continuous posterior probability distribution of rain rate. To advance the understanding of theoretical benefits of the Bayesian approach, sensitivity analyses have been conducted based on two synthetic datasets for which the “true” conditional and prior distribution are known. Results demonstrate that even when the prior and conditional likelihoods are specified perfectly, biased retrievals may occur at high rain rates. This bias is not the result of a defect of the Bayesian formalism, but rather represents the expected outcome when the physical constraint imposed by the radiometric observations is weak owing to saturation effects. It is also suggested that both the choice of the estimators and the prior information are crucial to the retrieval. In addition, the performance of the Bayesian algorithm herein is found to be comparable to that of other benchmark algorithms in real-world applications, while having the additional advantage of providing a complete continuous posterior probability distribution of surface rain rate.

A hyperstable neural network for the modelling and control of nonlinear systems

A multivariable hyperstable robust adaptive decoupling control algorithm based on a neural network is presented for the control of nonlinear multivariable coupled systems with unknown parameters and structure. The Popov theorem is used in the design of the controller. The modelling errors, coupling action and other uncertainties of the system are identified on-line by a neural network. The identified results are taken as compensation signals such that the robust adaptive control of nonlinear systems is realised. Simulation results are given.

Euler's theorem under the microscope

In this article Geoff Tennant summarises the first half of Imre Lakatos's seminal 1976 book, "Proofs and refutations: the logic of mathematical discovery". Implications are drawn for the classroom treatment of proof.

A concept of approximated densities for efficient nonlinear estimation

This paper presents the theoretical development of a nonlinear adaptive filter based on a concept of filtering by approximated densities (FAD). The most common procedures for nonlinear estimation apply the extended Kalman filter. As opposed to conventional techniques, the proposed recursive algorithm does not require any linearisation. The prediction uses a maximum entropy principle subject to constraints. Thus, the densities created are of an exponential type and depend on a finite number of parameters. The filtering yields recursive equations involving these parameters. The update applies the Bayes theorem. Through simulation on a generic exponential model, the proposed nonlinear filter is implemented and the results prove to be superior to that of the extended Kalman filter and a class of nonlinear filters based on partitioning algorithms.

Random-walk-based characterisation of multiple access interference in a DS/SSMA system

The problem of calculating the probability of error in a DS/SSMA system has been extensively studied for more than two decades. When random sequences are employed some conditioning must be done before the application of the central limit theorem is attempted, leading to a Gaussian distribution. The authors seek to characterise the multiple access interference as a random-walk with a random number of steps, for random and deterministic sequences. Using results from random-walk theory, they model the interference as a K-distributed random variable and use it to calculate the probability of error in the form of a series, for a DS/SSMA system with a coherent correlation receiver and BPSK modulation under Gaussian noise. The asymptotic properties of the proposed distribution agree with other analyses. This is, to the best of the authors' knowledge, the first attempt to propose a non-Gaussian distribution for the interference. The modelling can be extended to consider multipath fading and general modulation

Essential selfadjointness of singular magnetic Schrödinger operators on Riemannian manifolds

In this paper we extend the well-known Leinfelder–Simader theorem on the essential selfadjointness of singular Schrödinger operators to arbitrary complete Riemannian manifolds. This improves some earlier results of Shubin, Milatovic and others.

Correlations between two sets of angular relation equations

It is shown here that the angular relation equations between direct and reciprocal vectors are very similar to the angular relation equations in Euler's theorem. These two sets of equations are usually treated separately as unrelated equations in different fields. In this careful study, the connection between the two sets of angular equations is revealed by considering the cosine rule for the spherical triangle. It is found that understanding of the correlation is hindered by the facts that the same variables are defined differently and different symbols are used to represent them in the two fields. Understanding the connection between different concepts is not only stimulating and beneficial, but also a fundamental tool in innovation and research, and has historical significance. The background of the work presented here contains elements of many scientific disciplines. This work illustrates the common ground of two theories usually considered separately and is therefore of benefit not only for its own sake but also to illustrate a general principle that a theory relevant to one discipline can often be used in another. The paper works with chemistry related concepts using mathematical methodologies unfamiliar to the usual audience of mainstream experimental and theoretical chemists.

Noise propagation from a cutting of arbitrary cross-section and impedance

A boundary integral equation is described for the prediction of acoustic propagation from a monofrequency coherent line source in a cutting with impedance boundary conditions onto surrounding flat impedance ground. The problem is stated as a boundary value problem for the Helmholtz equation and is subsequently reformulated as a system of boundary integral equations via Green's theorem. It is shown that the integral equation formulation has a unique solution at all wavenumbers. The numerical solution of the coupled boundary integral equations by a simple boundary element method is then described. The convergence of the numerical scheme is demonstrated experimentally. Predictions of A-weighted excess attenuation for a traffic noise spectrum are made illustrating the effects of varying the depth of the cutting and the absorbency of the surrounding ground surface.

On the existence of two-dimensional Euler flows satisfying energy-Casimir stability criteria

The energy-Casimir stability method, also known as the Arnold stability method, has been widely used in fluid dynamical applications to derive sufficient conditions for nonlinear stability. The most commonly studied system is two-dimensional Euler flow. It is shown that the set of two-dimensional Euler flows satisfying the energy-Casimir stability criteria is empty for two important cases: (i) domains having the topology of the sphere, and (ii) simply-connected bounded domains with zero net vorticity. The results apply to both the first and the second of Arnold’s stability theorems. In the spirit of Andrews’ theorem, this puts a further limitation on the applicability of the method. © 2000 American Institute of Physics.

On nonlinear symmetric stability and the nonlinear saturation of symmetric instability

A nonlinear symmetric stability theorem is derived in the context of the f-plane Boussinesq equations, recovering an earlier result of Xu within a more general framework. The theorem applies to symmetric disturbances to a baroclinic basic flow, the disturbances having arbitrary structure and magnitude. The criteria for nonlinear stability are virtually identical to those for linear stability. As in Xu, the nonlinear stability theorem can be used to obtain rigorous upper bounds on the saturation amplitude of symmetric instabilities. In a simple example, the bounds are found to compare favorably with heuristic parcel-based estimates in both the hydrostatic and non-hydrostatic limits.

Nonlinear stability of continuously stratified quasi-geostrophic flow

Nonlinear stability theorems analogous to Arnol'd's second stability theorem are established for continuously stratified quasi-geostrophic flow with general nonlinear boundary conditions in a vertically and horizontally confined domain. Both the standard quasi-geostrophic model and the modified quasi-geostrophic model (incorporating effects of hydrostatic compressibility) are treated. The results establish explicit upper bounds on the disturbance energy, the disturbance potential enstrophy, and the disturbance available potential energy on the horizontal boundaries, in terms of the initial disturbance fields. Nonlinear stability in the sense of Liapunov is also established.

Crooks' fluctuation theorem for a process on a two dimensional fluid field

We investigate the behavior of a two-dimensional inviscid and incompressible flow when pushed out of dynamical equilibrium. We use the two-dimensional vorticity equation with spectral truncation on a rectangular domain. For a sufficiently large number of degrees of freedom, the equilibrium statistics of the flow can be described through a canonical ensemble with two conserved quantities, energy and enstrophy. To perturb the system out of equilibrium, we change the shape of the domain according to a protocol, which changes the kinetic energy but leaves the enstrophy constant. We interpret this as doing work to the system. Evolving along a forward and its corresponding backward process, we find numerical evidence that the distributions of the work performed satisfy the Crooks relation. We confirm our results by proving the Crooks relation for this system rigorously.

Nonlinear stability of Eady's model

A nonlinear stability theorem is established for Eady's model of baroclinic flow. In particular, the Eady basic state is shown to be nonlinearly stable (for arbitrary shear) provided (Δz)/(Δy) > 2(5)^1/2f/(πN),where Δz is the height of the domain, Δy the channel width, f the Coriolis parameter, and N the buoyancy frequency. When this criterion is satisfied, explicit bounds can be derived on the disturbance potential enstrophy, the disturbance energy, and the disturbance available potential energy on the rigid lids, which are expressed in terms of the initial disturbance fields. The disturbances are completely general (with nonzero potential vorticity) and are not assumed to be of small amplitude. The results may be regarded as an extension of Arnol'd's second nonlinear stability theorem to continuously stratified quasigeostrophic baroclinic flow.