Variational Monte Carlo study of core-valence separation schemes for first-row atoms and positive ions /

All-electron partitioning of wave functions into products ^core^vai of core and valence parts in orbital space results in the loss of core-valence antisymmetry, uncorrelation of motion of core and valence electrons, and core-valence overlap. These effects are studied with the variational Monte Carlo method using appropriately designed wave functions for the first-row atoms and positive ions. It is shown that the loss of antisymmetry with respect to interchange of core and valence electrons is a dominant effect which increases rapidly through the row, while the effect of core-valence uncorrelation is generally smaller. Orthogonality of the core and valence parts partially substitutes the exclusion principle and is absolutely necessary for meaningful calculations with partitioned wave functions. Core-valence overlap may lead to nonsensical values of the total energy. It has been found that even relatively crude core-valence partitioned wave functions generally can estimate ionization potentials with better accuracy than that of the traditional, non-partitioned ones, provided that they achieve maximum separation (independence) of core and valence shells accompanied by high internal flexibility of ^core and Wvai- Our best core-valence partitioned wave function of that kind estimates the IP's with an accuracy comparable to the most accurate theoretical determinations in the literature.

Histogram filtering as a tool in variational Monte Carlo optimization

Optimization of wave functions in quantum Monte Carlo is a difficult task because the statistical uncertainty inherent to the technique makes the absolute determination of the global minimum difficult. To optimize these wave functions we generate a large number of possible minima using many independently generated Monte Carlo ensembles and perform a conjugate gradient optimization. Then we construct histograms of the resulting nominally optimal parameter sets and "filter" them to identify which parameter sets "go together" to generate a local minimum. We follow with correlated-sampling verification runs to find the global minimum. We illustrate this technique for variance and variational energy optimization for a variety of wave functions for small systellls. For such optimized wave functions we calculate the variational energy and variance as well as various non-differential properties. The optimizations are either on par with or superior to determinations in the literature. Furthermore, we show that this technique is sufficiently robust that for molecules one may determine the optimal geometry at tIle same time as one optimizes the variational energy.

Variational Monte Carlo estimation of the dissociation energy of CuH using correlated sampling

A new approach to treating large Z systems by quantum Monte Carlo has been developed. It naturally leads to notion of the 'valence energy'. Possibilities of the new approach has been explored by optimizing the wave function for CuH and Cu and computing dissociation energy and dipole moment of CuH using variational Monte Carlo. The dissociation energy obtained is about 40% smaller than the experimental value; the method is comparable with SCF and simple pseudopotential calculations. The dipole moment differs from the best theoretical estimate by about 50% what is again comparable with other methods (Complete Active Space SCF and pseudopotential methods).

Region Connection Calculus: Composition Tables and Constraint Satisfaction Problems

Qualitative spatial reasoning (QSR) is an important field of AI that deals with qualitative aspects of spatial entities. Regions and their relationships are described in qualitative terms instead of numerical values. This approach models human based reasoning about such entities closer than other approaches. Any relationships between regions that we encounter in our daily life situations are normally formulated in natural language. For example, one can outline one's room plan to an expert by indicating which rooms should be connected to each other. Mereotopology as an area of QSR combines mereology, topology and algebraic methods. As mereotopology plays an important role in region based theories of space, our focus is on one of the most widely referenced formalisms for QSR, the region connection calculus (RCC). RCC is a first order theory based on a primitive connectedness relation, which is a binary symmetric relation satisfying some additional properties. By using this relation we can define a set of basic binary relations which have the property of being jointly exhaustive and pairwise disjoint (JEPD), which means that between any two spatial entities exactly one of the basic relations hold. Basic reasoning can now be done by using the composition operation on relations whose results are stored in a composition table. Relation algebras (RAs) have become a main entity for spatial reasoning in the area of QSR. These algebras are based on equational reasoning which can be used to derive further relations between regions in a certain situation. Any of those algebras describe the relation between regions up to a certain degree of detail. In this thesis we will use the method of splitting atoms in a RA in order to reproduce known algebras such as RCC15 and RCC25 systematically and to generate new algebras, and hence a more detailed description of regions, beyond RCC25.

Does Participation Matter ? The Impact of Subjective Calculus on Participation.

Rapport de recherche

A Variational Calculation of TE and TM Cutoff Wavenumbers in Circular Eccentric Guides by Conformal Mapping

The cutoff wavenumbers of higher order modes in circular eccentric guides are computed with the variational analysis combined with a conformal mapping. A conformal mapping is applied to the variational formulation, and the variational equation is solved by the finite-element method. Numerical results for TE and TM cutoff wavenumbers are presented for different distances between the centers and ratio of the radii. Comparisons with numerical results found in the literature validate the presented method

Topological Invariants in Hydrodynamics and Hydromagnetics

In this thesis we are studying possible invariants in hydrodynamics and hydromagnetics. The concept of flux preservation and line preservation of vector fields, especially vorticity vector fields, have been studied from the very beginning of the study of fluid mechanics by Helmholtz and others. In ideal magnetohydrodynamic flows the magnetic fields satisfy the same conservation laws as that of vorticity field in ideal hydrodynamic flows. Apart from these there are many other fields also in ideal hydrodynamic and magnetohydrodynamic flows which preserves flux across a surface or whose vector lines are preserved. A general study using this analogy had not been made for a long time. Moreover there are other physical quantities which are also invariant under the flow, such as Ertel invariant. Using the calculus of differential forms Tur and Yanovsky classified the possible invariants in hydrodynamics. This mathematical abstraction of physical quantities to topological objects is needed for an elegant and complete analysis of invariants.Many authors used a four dimensional space-time manifold for analysing fluid flows. We have also used such a space-time manifold in obtaining invariants in the usual three dimensional flows.In chapter one we have discussed the invariants related to vorticity field using vorticity field two form w2 in E4. Corresponding to the invariance of four form w2 ^ w2 we have got the invariance of the quantity E. w. We have shown that in an isentropic flow this quantity is an invariant over an arbitrary volume.In chapter three we have extended this method to any divergence-free frozen-in field. In a four dimensional space-time manifold we have defined a closed differential two form and its potential one from corresponding to such a frozen-in field. Using this potential one form w1 , it is possible to define the forms dw1 , w1 ^ dw1 and dw1 ^ dw1 . Corresponding to the invariance of the four form we have got an additional invariant in the usual hydrodynamic flows, which can not be obtained by considering three dimensional space.In chapter four we have classified the possible integral invariants associated with the physical quantities which can be expressed using one form or two form in a three dimensional flow. After deriving some general results which hold for an arbitrary dimensional manifold we have illustrated them in the context of flows in three dimensional Euclidean space JR3. If the Lie derivative of a differential p-form w is not vanishing,then the surface integral of w over all p-surfaces need not be constant of flow. Even then there exist some special p-surfaces over which the integral is a constant of motion, if the Lie derivative of w satisfies certain conditions. Such surfaces can be utilised for investigating the qualitative properties of a flow in the absence of invariance over all p-surfaces. We have also discussed the conditions for line preservation and surface preservation of vector fields. We see that the surface preservation need not imply the line preservation. We have given some examples which illustrate the above results. The study given in this thesis is a continuation of that started by Vedan et.el. As mentioned earlier, they have used a four dimensional space-time manifold to obtain invariants of flow from variational formulation and application of Noether's theorem. This was from the point of view of hydrodynamic stability studies using Arnold's method. The use of a four dimensional manifold has great significance in the study of knots and links. In the context of hydrodynamics, helicity is a measure of knottedness of vortex lines. We are interested in the use of differential forms in E4 in the study of vortex knots and links. The knowledge of surface invariants given in chapter 4 may also be utilised for the analysis of vortex and magnetic reconnections.

Studies of stability of fluid flowa using variational methods

The study of stability problems is relevant to the study of structure of a physical system. It 1S particularly important when it is not possible to probe into its interior and obtain information on its structure by a direct method. The thesis states about stability theory that has become of dominant importance in the study of dynamical systems. and has many applications in basic fields like meteorology, oceanography, astrophysics and geophysics- to mention few of them. The definition of stability was found useful 1n many situations, but inadequate in many others so that a host of other important concepts have been introduced in past many years which are more or less related to the first definition and to the common sense meaning of stability. In recent years the theoretical developments in the studies of instabilities and turbulence have been as profound as the developments in experimental methods. The study here Points to a new direction for stability studies based on Lagrangian formulation instead of the Hamiltonian formulation used by other authors.

Variational Wigner-Kirkwood approach to relativistic mean field theory

The recently developed variational Wigner-Kirkwood approach is extended to the relativistic mean field theory for finite nuclei. A numerical application to the calculation of the surface energy coefficient in semi-infinite nuclear matter is presented. The new method is contrasted with the standard density functional theory and the fully quantal approach.

Calculus Exam questions

Exam questions and solutions on a variety of calculus topics.

Further Calculus and Analysis

Notes, exercises, exam questions and solutions for a second year analysis course.

Calculus

Word notes for a first year university calculus course

Further Calculus and Algebra

Exercises and solutions for a first year calculus and algebra course. Diagrams for the questions are all together in the support.zip file, as .eps files

Advanced Calculus

Exercises and solutions for a third year calculus course. Diagrams for the questions are all together in the support.zip file, as .eps files

Vector Calculus

Exercises and solutions about vector calculus