Large-core potentials

There are several variations of this method. The PRDDO/M method is parameterized to reproduce electrostatic potentials. The PRDDO/M/FCP method uses frozen core potentials. PRDDO/M/NQ uses an approximation called not quite orthogonal orbitals in order to give efficient calculations on very large molecules. The results of these methods are fairly good overall, although bond lengths involving alkali metals tend to be somewhat in error. 

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. 

Many researchers have performed calculations that include the two large-magnitude components of the spinnors. This provides a balance between high accuracy and making the calculation tractable. Such calculations are often done on atoms in order to obtain the wave function description used to create relativistic core potentials. 

Ah initio methods pose problems due a whole list of technical difficulties. Most of these stem from the large number of electrons and low-energy excited state. Core potentials are often used for heavier elements to ease the computational requirements and account for relativistic elfects. 

Ah initio calculations with core potentials are usually the method of choice. The researcher must make a difficult choice between minimizing the CPU time requirements and obtaining more accurate results when deciding which core potential to use. Correlation is particularly difficult to include because of the large number of electrons even in just the valence region of these elements. 

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. 

After some experience with MNDO, it became clear that there were certain systematic en ors. For example the repulsion between two atoms which are 2-3 A apart is too high. This has as a consequence that activation energies in general are too large. The source was traced to too repulsive an interaction in the core-core potential. To remedy this, the core-core function was modified by adding Gaussian functions, and the whole model was reparameterized. The result was called Austin Model 1 (AMl) in honour of Dewar s move to the University of Austin. The core-core repulsion of AMI has the form ... 

Light wave technologies provide a number of special challenges for polymeric materials. Polymer fibers offer the best potential for optical communications in local area network (LAN) applications, because their large core size makes it relatively cheap to attach connectors to them. There is a need for polymer fibers that have low losses and that can transmit the bandwidths needed for LAN applications the aciylate and methacrylate polymers now under study have poor loss and bandwidth performance. Research on monomer purification, polymerization to precise molecular-size distributions, and weU-controlled drawing processes is relevant here. There is also a need for precision plastic molding processes for mass prodnction of optical fiber connectors and splice hardware. A tenfold reduction in the cost of fiber and related devices is necessaiy to make the utilization of optical fiber and related devices economical for local area networks and tlie telecommunications loop. 

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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