All-electron Dirac-Fock relativistic calculations on molecules containing heavy atoms such as Au or U are very time-consuming. A commonly used approach is to do [Pg.602]

Another approach is to do a nonrelativistic calculation, using, for example, the Hartree-Fock method, and then use perturbation theory to correct for relativistic effects. For perturbation-theory formulations of relativistic Hartree-Fock calculations and relativistic KS DFT calculations, see W. Kutzelnigg, E. Ottschofski, and R. Franke, J. Chem. Phys., 102,1740 (1995) and C. van Wiillen, J. Chem. Phys., 103,3589 (1995) 105,5485 (1996). [Pg.603]

Relativistic all-electron calculations on F2, CI2, Br2,12, and At2 using various correlation methods found that the relativistic corrections were approximately independent of the level of theory used, except for At2 [L. V sscher and K. G. Dyall, /. Chem. Phys., 104,9040 (1996)]. For example, with a valence triple-zeta polarized basis set, the changes in on going from a nonrelativistic to a relativistic calculation were -8,-7 -7, -7, -7 kcal/mol for Br2 using the HF, MP2, CISD, CCSD, CCSD(T) methods, respectively for I2, these changes were -15, -13, -12.5, -13, -13 kcal/mol for At2, they were -30, -27, -24, -25, -24 kcal/mol. [Pg.603]

The Effects of Relativity in Atoms, Molecules, and the Solid State, Plenum, 1991 J. Almlof and O. Gropen in K. B. Lipkowitz and D. B. Boyd (eds.). Reviews in Computational Chemistry, o. 8, Chapter 4. [Pg.604]

Results from fully relativistic calculations are scarce, and there is no clear consensus on which effects are the most important. The Breit (Gaunt) term is believed to be small and many relativistic calculations neglect this term, or include it as a perturbational term evaluated from the converged wave function. For geometries, the relativistic contraction of the s-orbitals normally means that bond lengths become shorter. [Pg.289]

Since working with the full four-component wave function is so demanding, various approximative methods have been developed where the small component of the wave function is eliminated to a certain order in 1/c or approximated (such as the Foldy-WouthuyseriJ or Douglas-Kroll transformations, thereby reducing the four-component wave function to only two components. A description of such methods is beyond the scope of this book. [Pg.289]

Advanced Molecular Quantum Mechanics, Chapman and Hall, 1973 P. Pyykko, Chem. Rev., 88 (1988), 563 J. Almlof, O. Gropen, Rev. Comp. Chem., 8 (1996), 203 K. Balasubramanian, Relativistic Effects in Chemistry, Wiley, 1997. [Pg.292]

McWeeny, Methods of Molecular Quantum Mec/iantcs, Academic Press, 1992 S. A. Perera, R. J. Bartlett, Quant. Chem., 49 (2005), 435. [Pg.292]

Relativistic quantum mechanics yields the same type of expressions for the isomer shift as the classical approach described earlier. Relativistic effects have to be considered for the calculation of the electron density. The corresponding contributions to i/ (0)p may amount to about 30% for iron, but much more for heavier atoms. In Appendix D, a few examples of correction factors for nonrelativistically calculated charge densities are collected. Even the nonrelativistically calculated p(0) values accurately follow the chemical variations and provide a reliable tool for the prediction of Mossbauer properties [16]. [Pg.81]

The Schrodinger equation is a nonrelativistic description of atoms and molecules. Strictly speaking, relativistic effects must be included in order to obtain completely accurate results for any ab initio calculation. In practice, relativistic effects are negligible for many systems, particularly those with light elements. It is necessary to include relativistic effects to correctly describe the behavior of very heavy elements. With increases in computer capability and algorithm efficiency, it will become easier to perform heavy atom calculations and thus an understanding of relativistic corrections is necessary. [Pg.261]

This chapter provides only a brief discussion of relativistic calculations. Currently, there is a small body of references on these calculations in the computational chemistry literature, with relativistic core potentials comprising the largest percentage of that work. However, the topic is important both because it is essential for very heavy elements and such calculations can be expected to become more prevalent if the trend of increasing accuracy continues. [Pg.261]

As the nuclei become heavier, the strong attraction of the electrons by the very large nuclear charge causes the electrons to move very rapidly and behave relativistically, i.e. their relative mass (m) increases according to equation 1, and the effective Bohr radius (ao) for inner electrons with large average speeds decreases according to equation 230. [Pg.9]

In equation 1, mo is the rest mass of the electron, v is the average electron speed and c is the speed of light (137 au) (1 — v/c)1/2 is the relativistic correction. The average speed for a Is electron at the nonrelativistic limit is Z au, where Z is the atomic number30. [Pg.9]

In equation 2, so is the permittivity of free space and e is the charge on the electron. [Pg.9]

FIGURE 2. Stabilization of the valence ns orbital due to the relativistic effect. Reproduced by permission of Gordon and Breach Science Publishers from Reference 5 [Pg.9]

The effect of relativity on various properties (e.g. ionization energies, electron affinity etc.) of the eka-lead element 114 in comparison to the other group 14 elements was studied recently by Schwerdtfeger and coworkers486. [Pg.10]

and 5642.32 ppm, respectively. Relativistic corrections to ff (atom) increase dramatically with atomic number, e.g., 1400 ppm for Z = 54. These relativistic values were calculated using a theory (RRPA) which reduces to the CHF technique in the nonrelativistic limit. We have used the above results to determine the relativistic free atom values shown in Table 1. It is important to keep relativistic effects in mind when the absolute shielding of nuclei of high atomic number are considered. On the other hand, relativistic corrections are largest for the k core, which is least disturbed when a heavy atom forms a molecule, so that relativistic effects on heavy atom chemical shifts may be considerably less than those on absolute shielding. [Pg.61]

A part of the relativistic corrections due to a heavy neighboring atom can be approximated by third-order perturbation theory with nonrelativistic functions. The contribution to shielding comes from the cross term involving the spin-orbit coupling, I S interaction, and the external field-orbit interaction. In nonrelativistic terms, the shielding mechanism is that the external field induces an orbital angular momentum on the electrons of the heavy atom (Br or I), this produces a polarization in the electron spin by spin-orbit coupling, and the spin polarization is transferred to the resonant nucleus by a Fermi contact and by a nuclear spin-electron spin dipolar [Pg.61]

These were calculated by the method of Barnes and Smith from spin-orbit splittings in atomic spectra without relativistic correction (open circles). Values calculated from relativistic Hartree-Fock-Slater atomic wave functions are included for comparison (filled circles). [Pg.61]

For the lighter chemical elements, the velocity of the electrons is negligible compared with the velocity of light. However, for the actinides and to a lesser extent the lanthanides this is not the case as the velocity of the electrons increases towards c, then their mass increases too. [Pg.152]

A important relativistic effect is that 5f orbitals of actinides are larger and their electrons more weakly bound than predicted by non-relativistic calculations, hence the 5f electrons are more chemically available . This leads to [Pg.152]

Question 9.14.5 x 10 tonnes of uranium is present in the Earth s oceans, at a concentration of 3.3 mg m (about 1/lOOOth that in the crust). How might it be extracted [Pg.152]

Question 9.2 What are the advantages of using UFefor isotope separation [Pg.152]

Answer 9.2 It vapourizes at low temperatures, so that little energy is used for that it has a low molecular mass, so that, since separation factors are proportional to the difference in mass between the and U-containing molecules, easier separations are achieved since fluorine is monoisotopic ( F), only molecules of two different masses are involved, minimizing overlap between and U-containing species (this would not be the case if, say. Cl or Br were involved). [Pg.152]

Because the s and p electrons penetrate the nucleus better than the d or f electrons do, the s and p electrons are accelerated to a greater extent. Thus, the [Pg.130]

As a result of relativistic orbital contraction, the atomic radius of Au is less than that expected on the basis of its periodic trends Cu (135 pm), Ag (160 pm), and Au (135 pm). Because of the small size of its half-filled 6s orbital, the E.A. of Au (223kJ/mol) is considerably larger than that for Ag (l26kJ/mol) orCu (I l8kJ/mol). In fact, the E.A. of Au is so large that gold exists as the Au anion in the compound cesium auride (CsAu). [Pg.131]

Valence orbital energies for Au and Hg in the absence of relativistic effects and with relativistic effects included. [Pg.132]

The group and periodic trends of ionization energies, atomic sizes and electronegativity coefficients are discussed above in terms of the variations in electronic configurations of the atoms. The values of these [Pg.91]

The theory of relativity expresses the relationship between the mass m of a particle travelling at a velocity r and its rest mass, [Pg.92]

Equation (4.8) contains the possible implication that element 137 would be the last in the series of elements, since any higher values of Z would have Is electron velocities greater than that of Ight. In a personal communication to the author. Professor Pekka Pyyko wrote The element 138 would be in trouble, IF the nuclei were points. In the exact Darwin-Gordon (1928) solution of the Dirac equation for a Coulomb potential, the lowest, is, eigenvalue (i.e. orbital energy) would dive Into the positron-llke continuum if Z c. [Pg.92]

A realistic finite nuclear size prevents this up to about Z = [Pg.92]

Equation (4.8) gives an estimate of the mass of the mercury Is electron as about 23% greater than its rest mass. Since the radius of the Is orbital is inversely proportional to the mass of the electron, the radius of the orbital is reduced by about 23% compared to that of the non-relativis-tic radius. This s orbital contraction affects the radii of all the other orbitals in the atom up to, and including, the outermost orbitals. The s orbitals contract, the p orbitals also contract, but the more diffuse d and f orbitals can become more diffuse as electrons in the contracted s and p orbitals offer a greater degree of shielding to any electrons in the d and f orbitals. [Pg.92]

Applications of fragmentation methods include calculations on proteins, protein-ligand binding, solids, and nanomaterials, and study of chemical reactions. The above-cited review noted that fragmentation methods are underused, due perhaps to uncertainty as to their accuracy. [Pg.581]

Relativistic DFT calculations on the solids PbO, PbS04, and Pb02 resulted in a standard emf for the lead storage cell of 2.13 V, quite close to the true value 2.11 V, whereas when relativistic effects were omitted, the calculation gave an emf of only 0.39 V [R. Ahuja et al., Phys. Rev. Lett., 106, 018301 (2011)]. [Pg.582]

Heavy-atom relativistic effects influence these shifts. [Pg.1447]

Pacchioni G, Chung S-C, Kruger S and Rdsch N 1997 Is CO chemisorbed on Pt anomalous compared with Ni and Pd An example of surface chemistry dominated by relativistic effects Surf. Sci. 392 173... [Pg.2235]

In this work, relativistic effects are included in the no-pah or large component only approximation [13]. The total electronic Hamiltonian is H (r R) = H (r R) + H (r R), where H (r R) is the nom-elativistic Coulomb Hamiltonian and R) is a spin-orbit Hamiltonian. The relativistic (nomelativistic) eigenstates, are eigenfunctions of R)(H (r R)). Lower (upper)... [Pg.452]

In summary, the techniques outlined in this work represent the first step on a path that will lead to increased understanding of, and more accurate computational approaches for treating, nonadiabatic processes in which relativistic effects cannot be neglected. [Pg.473]

B. A. Hess and C. M. Marian, Relativistic Effects in the Calculation of the Electronic Energy, in Computational Molecular Spectroscopy, P. Jensen and P. Bunker, eds., John Wiley Sc Sons, Inc., Chichester, UK, 2000, pp. 169-220. [Pg.473]

Unlike semiempirical methods that are formulated to completely neglect the core electrons, ah initio methods must represent all the electrons in some manner. However, for heavy atoms it is desirable to reduce the amount of computation necessary. This is done by replacing the core electrons and their basis functions in the wave function by a potential term in the Hamiltonian. These are called core potentials, elfective core potentials (ECP), or relativistic effective core potentials (RECP). Core potentials must be used along with a valence basis set that was created to accompany them. As well as reducing the computation time, core potentials can include the effects of the relativistic mass defect and spin coupling terms that are significant near the nuclei of heavy atoms. This is often the method of choice for heavy atoms, Rb and up. [Pg.84]

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. [Pg.262]

The use of RECP s is often the method of choice for computations on heavy atoms. There are several reasons for this The core potential replaces a large number of electrons, thus making the calculation run faster. It is the least computation-intensive way to include relativistic effects in ah initio calculations. Furthermore, there are few semiempirical or molecular mechanics methods that are reliable for heavy atoms. Core potentials were discussed further in Chapter 10. [Pg.262]

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. [Pg.263]

Relativistic effects are cited for changes in energy levels, resulting in the yellow color of gold and the fact that mercury is a liquid. Relativistic effects are also cited as being responsible for about 10% of lanthanide contraction. Many more specific examples of relativistic effects are reviewed by Pyykko (1988). [Pg.263]

K. Balasubramanian, Relativistic Effects in Chemistry John Wiley Sons, New York (1997). [Pg.265]

Core potentials are seldom used for organic molecules because there are so few electrons in the core. Relativistic effects are seldom included since they have very little effect on the result. Ah initio methods are discussed further in Chapter 3. [Pg.284]

The heavier elements are affected by relativistic effects. This is most often accounted for by using relativistic core potentials. Relativistic effects are discussed in more detail in Chapters 10 and 33. [Pg.285]

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. [Pg.286]

Relativistic effects are significant for the heavier metals. The method of choice is nearly always relativistically derived effective core potentials. Explicit spin-orbit terms can be included in ah initio calculations, but are seldom used because of the amount of computational effort necessary. Relativistic calculations are discussed in greater detail in Chapter 33. [Pg.289]

Relativistic effects should always be included in these calculations. Particularly common is the use of core potentials. If core potentials are not included, then another form of relativistic calculation must be used. Relativistic effects are discussed in more detail in Chapter 33. [Pg.289]

General Equation of Motion. Neglecting relativistic effects, the rate of accumulation of mass within a Cartesian volume element dx-dy-dz must equal the sum of the rates of inflow minus outflow. This is expressed by the equation of continuity ... [Pg.87]

Basis sets for atoms beyond the third row of the periodic table are handled somewhat differently. For these very large nuclei, electrons near the nucleus are treated in an approximate way, via effective core potentials (ECPs). This treatment includes some relativistic effects, which are important in these atoms. The LANL2DZ basis set is the best known of these. [Pg.101]

Predict the structure and frequencies for this compound using two or more different DFT functionals and the LANL2DZ basis set augmented by diffuse functions (this basis set also includes effective core potentials used to include some relativistic effects for K and Cs). How well does each functional reproduce the observed spectral data ... [Pg.133]

There is a nice point as to what we mean by the experimental energy. All the calculations so far have been based on non-relativistic quantum mechanics. A measure of the importance of relativistic effects for a given atom is afforded by its spin-orbit coupling parameter. This parameter can be easily determined from spectroscopic studies, and it is certainly not zero for first-row atoms. We should strictly compare the HF limit to an experimental energy that refers to a non-relativistic molecule. This is a moot point we can neither calculate molecular energies at the HF limit, nor can we easily make measurements that allow for these relativistic effects. [Pg.187]

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