Dirac Slater discrete variational method

A suitable computational approach for the investigation of electronic and geometric structures of transactinide compounds is the fully relativistic Dirac-Slater discrete-variational method (DS-DVM), in a modem version called the density functional theory (DFT) method, which was originally developed in the 1970s (Rosdn and Ellis 1975). It offers a good compromise between accuracy and computational effort. A detailed description can be found in Chapter 4 of this book. 

The most successful truly ab initio calculation is the Dirac-Slater Discrete Variational Method of Walch and Ellis [67]. This handles the relativistic part of the Hamiltonian more rigorously than other approaches, and illustrates the importance of the equatorial ligands in determining the energy of the first optical transitions. Furthermore, the use of an optical transition state calculation makes... 

The two relativistic four-component methods most widely used in calculations of superheavy elements are the no-(virtual)pair DF (Coulomb-Breit) coupled cluster technique (RCC) of Eliav, Kaldor, and Ishikawa for atoms (equation 3), and the Dirac-Slater discrete variational method (DS/DVM) by Fricke for atoms and molecules. " Fricke s DS/DVM code uses the Dirac equation (3) approximated by a Slater exchange potential (DFS), numerical relativistic atomic DS wavefunctions, and finite extension of the nuclei. DFS calculations for the superheavy elements from Z = 100 to Z = 173 have been tabulated by Fricke and Soff. A review on various local density functional methods applied in superheavy chemistry has been given by Pershina. ... 

Earlier, the intrinsically approximate 4c Dirac-Slater discrete variational, DS DV, code of Ellis and Rosen [90] with the Slater — —3C[3p(r)/87i] — 0.7 was used for calculations of transactinide compounds (see [6] for a review). Even though the method was inaccurate in calculating total and, hence, dissociation energies, it provided accurate IPs, EAs and electron transition energies. 

DF=Dirac-Fock DFS = Dirac-Fock-Slater DS = Dirac-Slater DVM = discrete variational method EC = electron capture MCDF = multi-configuration DF NR = nonrelativis-... 

To elucidate the nature of chemical bonding in metal carbides with the NaCl structure, the valence electronic states for TiC and UC have been calculated using the discrete-variational (DV) Xa method. Since relativistic effects on chemical bonding of compounds containing uranium atom become significant, the relativistic Hamiltonian, i.e., the DV-Dirac-Slater method, was used for UC. The results... 

Relativistic molecular orbital calculations have been performed for the study of the atomic-number dependence of the relativistic effects on chemical bonding by examining the hexafluorides XFg (X=S, Se, Mo, Ru, Rh, Te, W, Re, Os, hr, Pt, U, Np, Pu) and diatomic molecules (CuH, AgH, AuH), using the discrete-variational Dirac-Slater and Hartree-Fock-Slater methods. The conclusions obtained in the present work are sununarized. 

The aim of the present work is to perform a detailed theoretical study of the electronic structures of actinyl nitrates. Relativistic effects are remarkable in the electronic structure and chemical bonding of heavy atoms such as actinide elements[6j. In our previous study, we applied the relativistic discrete variational Dirac-Fock-Slater(DV-DFS) method to study of the electronic structure of uranyl nitrate dihydrate[7]. The accuracy of the DV-DFS method was demonstrate by its ability to reproduce the uranyl nitrate dihydrate experimental X-ray photoelectron spectrum. 

Methods DHF, Dirac-Hartreer-Fock DHFS, Dirac-Hartree-Fock-Slater HF, Hartree-Fock OCE, one-center expansion MS, multiple-scattering DV, discrete-variational QR, quasirelativistic INDO, intermediate neglect of differential overlap WHT, Wolfsberg-Helmholz QR-EHT, quasirelativistic two-component extended Httckel EHT, extended Hllckel. 

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