Pseudopotentials relativistic

To summarize, the RPPA is a method that can accurately describe relativistic effects, even though the relativistic perturbation operator used in the pseudopotential procedure is acting on the valence space and not the region dose to the nudeus, as this is the case for the correct all-electron relativistic perturbation operator. That is, relativistic effects are completely transferred into the valence space. These effects are also completely transferable from the atomic to the molecular case as the results for Au2 show. If relativistic pseudopotentials are carefully adjusted, they can produce results with errors much smaller than the errors originating from basis set incompleteness, basis set superposition or from the electron correlation procedure applied. 

Table4.6 Lattice constants a, volume V, cohesive energy and bulk modulus 6 for fee gold from nonrelativistic and relativistic pseudopotential DFT calculations (from Ref [402]).

Schwerdtfeger, P. (2003) Relativistic Pseudopotentials, in Theoretical Chemistry and Physics of Heavy and Superheavy Elements, Vol. 11 (eds U. Kaldor and S. Wilson), Progress in Theoretical Chemistry and Physics, Kluwer, Dordrecht, pp. 399—438. in references therein. 

Pyykko, P. and Stoll, H. (2000) Relativistic pseudopotential calculations, 1993-June 1999. in R.S.C. Specialist Periodical Reports, Chemical Modelling, Applications and Theory, Vol. 1, pp. 239-305. 

Han, Y.-K. and Hirao, K. (2000) On the transferability of relativistic pseudopotentials in density-functional calculations AuH, AuCl, and Au2. Chemical Physics Letters, 324, 453-458. 

Pyykkd, P. and Zhao, Y.-F. (1991) Ab initio calculations on the (ClAuPH )2 dimer with relativistic pseudopotential Is the aurophilic attraction a correlation effect Angewandte Chemie International Edition, 30, 604—605. 

New correlation consistent basis sets have been developed for Y and Hg in conjunction with accurate small-core relativistic pseudopotentials. A few allelectron basis sets have also been optimized both with and without the inclusion... 

At MP2/VTZ + D + P. Quasi-relativistic pseudopotentials were used for Si, Ge, Sn, Pb, from Ref. 93. At MP2/CEP. Compact effective core potentials (CEPs) were used for C and Si. Their relativistic counterparts (RCEP) were used for Ge, Sn and Pb. Correction for basis set superposition errors is included, from Ref. 95. 

At MP4SDQ with a quasi-relativistic pseudopotential for Pb from Reference 44. 

Calculated at B3LYP/DZ+P. The core electrons of all group 14 elements were replaced by quasi-relativistic pseudopotentials. KRS = Kapp, Remko and Schleyer from... 

At MP2/VDZ+P, quasi-relativistic pseudopotentials were used for Si to Pb from Reference 473. cAt MP2/6-31G(d) from Reference 4. 

The preferential binding of the antitumour drug cisplatin (ds-diamminechloroplatinum-II) to GpG and ApG sequences in DNA has prompted the use of ab initio calculations with relativistic pseudopotentials to evaluate three important parameters for the Pt-adenine model complex [Pt(NH3)3 adenine]. These are the force constant for the Pt—N-7 bond bending out of the adenine... 

The first calculation of the complete hydroformylation cycle with Rh-phosphine catalysts (substrate = ethylene, model ligand = PH3) was published in 1997 [3]. The QM methods used are HF and MP2, respectively (cf. Section 3.1.2.1). Hybrid DFT methods such as B3LYP [4], however, are more appropriate in terms of both accuracy and efficiency [5, 6] (cf. Section 3.1.2.1). Therefore, the same model system was recalculated [7] on the level B3LYP functional/DZVP basis set [8]/quasi-relativistic pseudopotentials on rhodium [9]. Since homologous Ir catalysts are interesting alternatives from an economic point of view [10], calculations with the central metal Ir were also made. This comparative treatment is supported by the experimental assumption of a common mechanism [11], which equals the Heck-Breslow mechanism of the cobalt-catalyzed reaction [12],... 

Spin-orbit (SO) coupling corrections were calculated for the Pt atom since the relativistic effects are essential for species containing heavy elements. Other scalar relativistic corrections like the Darwin and mass-velocity terms are supposed to be implicitly included in (quasi)relativistic pseudopotentials because they mostly affect the core region of the considered heavy element. Their secondary influence can be seen in the contraction of the outer s-orbitals and the expansion of the d-orbitals. This is considered in the construction of the pseudoorbitals. The effective SO operator can be written within pseudopotential (PS) treatment in the form71 75... 

A comparison of different methods was undertaken for the hydride of element 111 (Seth et al. 1996). The conclusion of this study was that Dirac-Fock calculations, all-electron DKH calculations and relativistic pseudopotential calculations give very similar results, showing that relativistic effects are also well described in the more approximate methods. A large relativistic bond length contraction of about 50 pm was found, which makes the bond length of (111)H even slightly shorter than that of AuH, which is 152.4 pm, with a relativistic effect of the order of 20 pm (see Kaldor and Hess 1994). 

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