Theoretical studies of electric quadrupole transition probabilities in Mg II

The relativistic coupled cluster theory is employed to calculate electric quadrupole (E2) transition probabilities among the doublet states of Mg II which are of interest in astrophysical problems. This is the first time a highly correlated fully ab initio method has been used to compute these quantities for this particular ion. The line strengths and transition probabilities of a number of different transitions are reported and compared with those available in the literature.Received: 4 June 2003, Published online: 30 September 2003PACS: 31.10. + z Theory of electronic structure, electronic transitions, and chemical bindingSonjoy Majumder: Present address: Institut für Theoretische Chemie, Technische Universität München, 85747 Garching, Germany.     

Many-body effects in hyperfine interactions in <Superscript>205</Superscript>Pb<Superscript>+</Superscript>

Ab initio calculations have been carried out to study the magnetic dipole and electric quadrupole hyperfine structure constants of ²⁰⁵Pb⁺. Many-body effects have been considered to all orders using the relativistic coupled-cluster theory in the singles, doubles and partial triples approximation. The trends of these effects are found to be different from atomic systems that have been studied earlier.     

Effective and efficient characterization of lubrication flow over soft coatings

This work models the fluid-structure interactions associated with separating a solid from a soft elastic film in a liquid environment. One side of the soft film is permanently attached to a rigid substrate. The ensuing liquid flow and elastic deformations are derived by considering a system of partial differential equations, that govern the mechanics of the separation process. A finite element based computational scheme is developed to solve the governing equations and predict the resultant forces acting on the solid. It is shown that the resulting forces are influenced by the elasticity of the film for an initial duration and by the viscosity of the liquid at larger times. The proposed model is utilized to shed insights into the mechanics of the separation process in constrained-surface stereolithography process.

     

Efficient treatment of the Hartree interaction in the relativistic Kohn-Sham problem

We elaborate the two-component Douglas-Kroll reduction of the Dirac-Kohn-Sham problem of relativistic density-functional theory as introduced by Matveev and Rosch [J. Chem. Phys. 118, 3997 (2003)]. That method retains corrections to the Coulomb self-interaction (or Hartree) term of the energy functional that are due to the picture change. Using analytic expressions for the matrix elements, one is able to abandon the resolution of the identity approach for a crucial step of the relativistic transformation. Thus, a major source of uncertainties of the method is eliminated because basis sets no longer have to be extended by functions of higher angular momentum, previously required to ensure kinetic balance. This approach also relies on the electron charge-density fitting scheme via an auxiliary basis set. An efficient approximate implementation results if one restricts the relativistic transformation to the spherically symmetric atom-centered auxiliary functions. It provides accurate results while simplifying greatly the expressions for the matrix elements of the relativistically transformed operators and significantly reducing the computational effort. We demonstrate the performance of the method for the fine structure of one-electron levels of the Hg atom, the g-tensor shifts of NO2, and the properties of the diatomic molecules Bi2, Pb2, PbO, and TlH.     

Polynomial chaos representation of spatio-temporal random fields from experimental measurements

Two numerical techniques are proposed to construct a polynomial chaos (PC) representation of an arbitrary second-order random vector. In the first approach, a PC representation is constructed by matching a target joint probability density function (pdf) based on sequential conditioning (a sequence of conditional probability relations) in conjunction with the Rosenblatt transformation. In the second approach, the PC representation is obtained by having recourse to the Rosenblatt transformation and simultaneously matching a set of target marginal pdfs and target Spearman’s rank correlation coefficient (SRCC) matrix. Both techniques are applied to model an experimental spatio-temporal data set, exhibiting strong non-stationary and non-Gaussian features. The data consists of a set of oceanographic temperature records obtained from a shallow-water acoustics transmission experiment [1]. The measurement data, observed over a finite denumerable subset of the indexing set of the random process, is treated as a collection of observed samples of a second-order random vector that can be treated as a finite-dimensional approximation of the original random field. A set of properly ordered conditional pdfs, that uniquely characterizes the target joint pdf, in the first approach and a set of target marginal pdfs and a target SRCC matrix, in the second approach, are estimated from available experimental data. Digital realizations sampled from the constructed PC representations based on both schemes capture the observed statistical characteristics of the experimental data with sufficient accuracy. The relative advantages and disadvantages of the two proposed techniques are also highlighted.