Parameterization relativistic effects

The most common way of including relativistic effects in a calculation is by using relativisticly parameterized effective core potentials (RECP). These core potentials are included in the calculation as an additional term in the Hamiltonian. Core potentials must be used with the valence basis set that was created for use with that particular core potential. Core potentials are created by htting a potential function to the electron density distribution from an accurate relativistic calculation for the atom. A calculation using core potentials does not have any relativistic terms, but the effect of relativity on the core electrons is included. 

Molecular mechanics and semiempirical calculations are all relativistic to the extent that they are parameterized from experimental data, which of course include relativistic effects. There have been some relativistic versions of PM3, CNDO, INDO, and extended Huckel theory. These relativistic semiempirical calculations are usually parameterized from relativistic ah initio results. 

Nearly every technical difficulty known is routinely encountered in transition metal calculations. Calculations on open-shell compounds encounter problems due to spin contamination and experience more problems with SCF convergence. For the heavier transition metals, relativistic effects are significant. Many transition metals compounds require correlation even to obtain results that are qualitatively correct. Compounds with low-lying excited states are difficult to converge and require additional work to ensure that the desired states are being computed. Metals also present additional problems in parameterizing semi-empirical and molecular mechanics methods. 

Most common among the approximate spin-orbit Hamiltonians are those derived from relativistic effective core potentials (RECPs).35-38 Spin-orbit coupling operators for pseudo-potentials were developed in the 1970s.39 40 In the meantime, different schools have devised different procedures for tailoring such operators. All these procedures to parameterize the spin-orbit interaction for pseudo-potentials have one thing in common The predominant action of the spin-orbit operator has to be transferred from... 

Two methods are mainly responsible for the breakthrough in the application of quantum chemical methods to heavy atom molecules. One method consists of pseudopotentials, which are also called effective core potentials (ECPs). Although ECPs have been known for a long time, their application was not widespread in the theoretical community which focused more on all-electron methods. Two reviews which appeared in 1996 showed that well-defined ECPs with standard valence basis sets give results whose accuracy is hardly hampered by the replacement of the core electrons with parameterized mathematical functions" . ECPs not only significantly reduce the computer time of the calculations compared with all-electron methods, they also make it possible to treat relativistic effects in an approximate way which turned out to be sufficiently accurate for most chemical studies. Thus, ECPs are a very powerful and effective method to handle both theoretical problems which are posed by heavy atoms, i.e. the large number of electrons and relativistic effects. 

Replace the core electrons by a potential parameterized by expansion into a suitable set of analytical functions of the nuclear-electron distance, for example a polynomial or a set of spherical Bessel or Gaussian functions. Since relativistic effects are mainly important for the core electrons, this potential can effectively include relativity. The potential may be different for each angular momentum. 

One way to reduce the computational cost of DFT (or WFT) calculations is to recognize that the core electrons of an atom have only an indirect influence on the atom chemistry. It thus makes sense to look for ways to precompute the atomic cores, essentially factoring them out of the larger electronic structure problem. The simplest way to do this is to freeze the core electrons, or to not allow their density to vary from that of a reference atom. This frozen core approach is generally more computationally efficient. One class of frozen core methods is the pseudopotential (PP) approach. The pseudopotential replaces the core electrons with an effective atom-centered potential that represents their influence on valence electrons and allows relativistic effects important to the core electrons to be incorporated. The advent of ultrasoft pseudopotentials (US-PPs) [18] enabled the explosion in supercell DFT calculations we have seen over the last 15 years. The projector-augmented wave (PAW) [19] is a less empirical and more accurate and transferable approach to partitioning the relativistic core and valence electrons and is also widely used today. Both the PP and PAW approaches require careful parameterizations of each atom type. 

One should also mention the relativistic effective core potentials. Typically, the most important relativistic effects in heavy elements are due to the contraction of the core orbitals. However, in those heavy elements, one often tries to avoid including all the valence electrons in an ab initio calculation, treating them instead with an effective core potential (ECP). Since the ECP is simply a parameterized potential included in a valence-only calculation, there is no extra cost associated with letting that potential describe a core that has a relativistically correct size, rather than a nonrelativistic one. 

Effective core potentials implicit treatment of core electrons in high-Z atoms with partial inclusion of relativistic effects through parameterization. 

A description of nuclear matter as an ideal mixture of protons and neutrons, possibly in (5 equilibrium with electrons and neutrinos, is not sufficient to give a realistic description of dense matter. The account of the interaction between the nucleons can be performed in different ways. For instance we have effective nucleon-nucleon interactions, which reproduce empirical two-nucleon data, e.g. the PARIS and the BONN potential. On the other hand we have effective interactions like the Skyrme interaction, which are able to reproduce nuclear data within the mean-field approximation. The most advanced description is given by the Walecka model, which is based on a relativistic Lagrangian and models the nucleon-nucleon interactions by coupling to effective meson fields. Within the relativistic mean-field approximation, quasi-particles are introduced, which can be parameterized by a self-energy shift and an effective mass. 

In order to overcome these problems, the core electrons are often excluded from the calculation (frozen-core approximation), and their effect on the valence electrons is parameterized in the form of a pseudo potential based on a relativistic atomic calculation [12]. In connection with GTO basis sets, the most common form of pseudo potential is the effective core potential (ECP) using Gaussian-type radial functions to describe the potential [13-16]. 

Effective core potential, REX, and relativistically parameterized semiempirical molecular orbital calculations are used to understand inter- and intramolecular bonding and how it relates to thermochromism in bibismuthines. All the calculations suggest modest secondary intermolecular Bi Bi bonding <930M343>. 

It is obvious that more sophisticated relativistic many-body methods should be used for correct treating the NEET effect. Really, the nuclear wave functions have the many-body character (usually, the nuclear matrix elements are parameterized according to the empirical data). The correct treating of the electron subsystem processes requires an account of the relativistic, exchange-correlation, and nuclear effects. Really, the nuclear excitation occurs by electron transition from the M shell to the K shell. So, there is the electron-hole interaction, and it is of a great importance a correct account for the many-body correlation effects, including the intershell correlations, the post-act interaction of removing electron and hole. 

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