Orbital specific types

If we want to determine the specific type of orbital transformation for this transition, we will need to examine the molecular orbitals for the largest components of the transition, indicated by the largest wavefunction coefficients. In this case, this is the relevant entry ... 

We generate hybrid orbitals on inner atoms whose bond angles are not readily reproduced using direct orbital overlap with standard atomic orbitals. Consequently, each of the electron group geometries described in Chapter 9 is associated with its own specific set of hybrid orbitals. Each type of hybrid orbital scheme shares the characteristics described in our discussion of methane ... 

The steric number of an inner atom determines the electron group geometry, each of which is associated with one specific type of hybrid orbital. 

It is not possible to use normal AO basis sets in relativistic calculations The relativistic contraction of the inner shells makes it necessary to design new basis sets to account for this effect. Specially designed basis sets have therefore been constructed using the DKH Flamiltonian. These basis sets are of the atomic natural orbital (ANO) type and are constructed such that semi-core electrons can also be correlated. They have been given the name ANO-RCC (relativistic with core correlation) and cover all atoms of the Periodic Table.36-38 They have been used in most applications presented in this review. ANO-RCC are all-electron basis sets. Deep core orbitals are described by a minimal basis set and are kept frozen in the wave function calculations. The extra cost compared with using effective core potentials (ECPs) is therefore limited. ECPs, however, have been used in some studies, and more details will be given in connection with the specific application. The ANO-RCC basis sets can be downloaded from the home page of the MOLCAS quantum chemistry software (http //www.teokem.lu.se/molcas). 

As indicated earlier, some drugs are bioactivated to reactive intermediates that interact with cellular constituents. One specific type of reactive substance mentioned previously is the free radical. Free radicals are highly reactive chemical species containing, in the outermost or bonding orbital, a single unpaired electron. As a result, this is an... 

In second quantization, the numerical vector-coupling coefficients (the Aff and ) appear as matrix elements of creation and annihilation operators X] and jc> The operator X creates an electron in an orthonormal spin orbital io), where /(j) = /) (j), and (T = a or p. Similarly, operator destroys an electron in the orthonormal spin orbital ia). In quantum chemistry problems in which the number of particles is conserved, the Xj and will always occur in pairs. The role of these operators is easily illustrated by showing their operation on a specific type of CSF, namely a Slater determinant. Thus, as an example, for the determinant... 

We have now considered three viewpoints from which thermal electrocyclic processes can be analyzed symmetry characteristics of the frontier orbitals, orbital correlation diagrams, and transition-state aromaticity. All arrive at the same conclusions about stereochemistiy of electrocyclic reactions. Reactions involving 4n + 2 electrons will be disrotatory and involve a Hiickel-type transition state, whereas those involving 4n electrons will be conrotatory and the orbital array will be of the Mobius type. These general principles serve to explain and correlate many specific experimental observations made both before and after the orbital symmetry mles were formulated. We will discuss a few representative examples in the following paragraphs. 

The use of Polya s Theorem in a specialized context such as the above, has led to the extension of the theorem along certain useful lines. One such derivation pertains to the situation where the boxes are not all filled from the same store of figures. More specifically, the boxes are partitioned into a number of subsets, and there is a store of figures peculiar to each subset. To make sense of this we must assume that no two boxes in different subsets are in the same orbit of the group in question. A simple extension of Polya s Theorem enables us to tackle problems of this type. Instead of the cycle index being a function of a single family of variables, the 5j, we have other families of variables, one for each subset. An example from chemical enumeration will make this clear. 

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