Force constants and dipole‐moment derivatives of molecules from perturbed Hartree–Fock calculations

General expressions for the force constants and dipole‐moment derivatives of molecules are derived, and the problems arising in their practical application are reviewed. Great emphasis is placed on the use of the Hartree–Fock function as an approximate wavefunction, and a number of its properties are discussed and re‐emphasised. The main content of this paper is the development of a perturbed Hartree–Fock theory that makes possible the direct calculation of force constants and dipole‐moment derivatives from SCF–MO wavefunctions. Essentially the theory yields ∂ϕi / ∂RJα, the derivative of an MO with respect to a nuclear coordinate.

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.

Determination of the vibrational transition moment ratio for the Coriolis interacting v9 and v10 fundamentals of allene

Comparison between observed and calculated infrared band contours has been made to determine the vibrational transition moment ratio |M10/M9| for the Coriolis interacting ν9 and ν10 perpendicular fundamentals of allene-h4. The ratio obtained is appreciably lower than that of a previous estimate and the result obtained by integrated band intensity measurements of Overend and Crawford. From the best estimate of the ratio, the dipole moment derivatives of the two bands are determined; the value for the weaker band ν9 is subject to a large uncertainty.

Characterising the variability and extremes of the stratospheric polar vortices using 2D moment analysis

The mean state, variability and extreme variability of the stratospheric polar vortices, with an emphasis on the Northern Hemisphere vortex, are examined using 2-dimensional moment analysis and Extreme Value Theory (EVT). The use of moments as an analysis to ol gives rise to information about the vortex area, centroid latitude, aspect ratio and kurtosis. The application of EVT to these moment derived quantaties allows the extreme variability of the vortex to be assessed. The data used for this study is ECMWF ERA-40 potential vorticity fields on interpolated isentropic surfaces that range from 450K-1450K. Analyses show that the most extreme vortex variability occurs most commonly in late January and early February, consistent with when most planetary wave driving from the troposphere is observed. Composites around sudden stratospheric warming (SSW) events reveal that the moment diagnostics evolve in statistically different ways between vortex splitting events and vortex displacement events, in contrast to the traditional diagnostics. Histograms of the vortex diagnostics on the 850K (∼10hPa) surface over the 1958-2001 period are fitted with parametric distributions, and show that SSW events comprise the majority of data in the tails of the distributions. The distribution of each diagnostic is computed on various surfaces throughout the depth of the stratosphere, and shows that in general the vortex becomes more circular with higher filamentation at the upper levels. The Northern Hemisphere (NH) and Southern Hemisphere (SH) vortices are also compared through the analysis of their respective vortex diagnostics, and confirm that the SH vortex is less variable and lacks extreme events compared to the NH vortex. Finally extreme value theory is used to statistically mo del the vortex diagnostics and make inferences about the underlying dynamics of the polar vortices.

Harringtonian virtue: Harrington, Machiavelli, and the method of the 'Moment'

This article presents a reinterpretation of James Harrington's writings. It takes issue with J. G. A. Pocock's reading, which treats him as importing into England a Machiavellian ‘language of political thought’. This reading is the basis of Pocock's stress on the republicanism of eighteenth-century opposition values. Harrington's writings were in fact a most implausible channel for such ideas. His outlook owed much to Stoicism. Unlike the Florentine, he admired the contemplative life; was sympathetic to commerce; and was relaxed about the threat of ‘corruption’ (a concept that he did not understand). These views can be associated with his apparent aims: the preservation of a national church with a salaried but politically impotent clergy; and the restoration of the royalist gentry to a leading role in English politics. Pocock's hypothesis is shown to be conditioned by his method; its weaknesses reflect some difficulties inherent in the notion of ‘languages of thought’.

First order k-th moment finite element analysis of nonlinear operator equations with stochastic data

We develop and analyze a class of efficient Galerkin approximation methods for uncertainty quantification of nonlinear operator equations. The algorithms are based on sparse Galerkin discretizations of tensorized linearizations at nominal parameters. Specifically, we consider abstract, nonlinear, parametric operator equations J(\alpha ,u)=0 for random input \alpha (\omega ) with almost sure realizations in a neighborhood of a nominal input parameter \alpha _0. Under some structural assumptions on the parameter dependence, we prove existence and uniqueness of a random solution, u(\omega ) = S(\alpha (\omega )). We derive a multilinear, tensorized operator equation for the deterministic computation of k-th order statistical moments of the random solution's fluctuations u(\omega ) - S(\alpha _0). We introduce and analyse sparse tensor Galerkin discretization schemes for the efficient, deterministic computation of the k-th statistical moment equation. We prove a shift theorem for the k-point correlation equation in anisotropic smoothness scales and deduce that sparse tensor Galerkin discretizations of this equation converge in accuracy vs. complexity which equals, up to logarithmic terms, that of the Galerkin discretization of a single instance of the mean field problem. We illustrate the abstract theory for nonstationary diffusion problems in random domains.

The full infinite dimensional moment problem on semi-algebraic sets of generalized functions

We consider a generic basic semi-algebraic subset S of the space of generalized functions, that is a set given by (not necessarily countably many) polynomial constraints. We derive necessary and sufficient conditions for an infinite sequence of generalized functions to be realizable on S, namely to be the moment sequence of a finite measure concentrated on S. Our approach combines the classical results about the moment problem on nuclear spaces with the techniques recently developed to treat the moment problem on basic semi-algebraic sets of Rd. In this way, we determine realizability conditions that can be more easily verified than the well-known Haviland type conditions. Our result completely characterizes the support of the realizing measure in terms of its moments. As concrete examples of semi-algebraic sets of generalized functions, we consider the set of all Radon measures and the set of all the measures having bounded Radon–Nikodym density w.r.t. the Lebesgue measure.

A moment problem for random discrete measures

Let X be a locally compact Polish space. A random measure on X is a probability measure on the space of all (nonnegative) Radon measures on X. Denote by K(X) the cone of all Radon measures η on X which are of the form η =