Core Potential-Based Method

Model core potential (MCP) methods replace core orbitals by a potential just as in ECP. On the other hand, MCP valence orbitals preserve the nodal structure of valence orbitals, unlike ECP valence orbitals. The expectation values of (r ) for the valence orbitals show that the results of MCP are closer to those calculated with all-electron orbitals when comparing MCP, ECP, and the all electron case. Comparisons between MCP and an all electron basis utilizing the full Breit-Pauli spin-orbit Hamiltonian based on multiconfigura-tional quasidegenerate perturbation theory (MCQDPT) calculations show good agreement between the two methods for hydrides of P, As, and Sb. The MCP based spin-orbit calculation appears to be a promising technique, but systematic studies of many different molecular systems are still needed to assess its characteristics and accuracy. 

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Ab initio methods for lanthanide and actinide molecules are mostly based on the effective core potential (ECP) method, especially if the molecules in question have several heavy atoms. The philosophy of the ECP method is to replace the chemically unimportant core electrons by an effective core potential and treat the remaining valence electrons explicitly. There are several techniques to derive RECPs which we now briefly describe and refer to the reviews by Christiansen et al. (1985), Krauss and Stevens (1984), Balasubramanian and Pitzer (1987) for further details. 

The only calculation we found for CdH is the work of Balasubramanian [68], using Cl with relativistic effective core potentials. The coupled-cluster results are presened in Table 6. Calculated values for R , cOg and Dg agree very well with experiment. Relativity contracts the bond by 0.04 and reduces the binding energy by 0.16 eV. The one- and two-component DK method reproduce the relativistic effects closely. Similar trends are observed for the excited states (Tables 7-9). Comparison with experiment is difficult for these states, since many of the experimental values are based on incomplete or uncertain data [65]. Calculated results for the CdH anion are shown in Table 10. The... 

The results presented here show that quantum-chemistry methods, whose accuracy and sophistication continue to increase, are capable of providing thermochemical data of practical value for modehng organometallic tin chemistry. In particular, the relativistic effective core potential used here appears to provide an adequate description of the electronic structure at tin, based on the favorable comparisons between experimental heats of formation and values predicted by the ECP/BAC-MP4 method. Trends in heats of... 

Model potential methods and their utilization in atomic structure calculations are reviewed in [139], main attention being paid to analytic effective model potentials in the Coulomb and non-Coulomb approximations, to effective model potentials based on the Thomas-Fermi statistical model of the atom, as well as employing a self-consistent field core potential. Relativistic effects in model potential calculations are discussed there, too. Paper [140] has examples of numerous model potential calculations of various atomic spectroscopic properties. 

Before any computational study on molecular properties can be carried out, a molecular model needs to be established. It can be based on an appropriate crystal structure or derived using any technique that can produce a valid model for a given compound, whether or not it has been prepared. Molecular mechanics is one such technique and, primarily for reasons of computational simplicity and efficiency, it is one of the most widely used technique. Quantum-mechanical modeling is far more computationally intensive and until recently has been used only rarely for metal complexes. However, the development of effective-core potentials (ECP) and density-functional-theory methods (DFT) has made the use of quantum mechanics a practical alternative. This is particularly so when the electronic structures of a small number of compounds or isomers are required or when transition states or excited states, which are not usually available in molecular mechanics, are to be investigated. However, molecular mechanics is still orders of magnitude faster than ab-initio quantum mechanics and therefore, when large numbers of... 

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