Electron correlation main group atoms

This is the simplest case. It is usually sufficient to have the valence orbitals active, perhaps with added Rydberg type orbitals for studies of excited states. One can normally leave the ns orbital inactive for main group atoms with more than three np electrons. First row transition metals are, however, more demanding. It has been shown that in order to be able to accurately describe the relative correlation effects in atomic states, which differ in the number of 3d electrons, one needs to use two sets of d-orbitals, 3d and 3d where the second set describes the strong radial correlation effects in the 3d shell [29]. Adding the 4s and 4p orbital one is faced with an active space of 14 orbitals. The importance of the second 3d orbital decreases for second and, in particular, for third row transition metals. 

In the past decade more efficient code and faster computers have allowed the use of electron-correlated methods of calculation and this has opened this area of theoretical chemistry to a wide range of research groups. The present sequel will be focused mainly on recent theoretical studies on a variety of oxidative processes involving oxygen atom transfer. We will include an extensive description of the very recent chemistry of peroxyni-trous acid (HO—ONO), dioxiranes, peracids and alkyl hydroperoxides. Since chemically realistic molecular systems can now be treated at an adequate level of electron-correlated... 

These properties of the d-shell chromophore (group) prove the necessity of the localized description of d-electrons of transition metal atom in TMCs with explicit account for effects of electron correlations in it. Incidentally, during the time of QC development (more than three quarters of century) there was a period when two directions based on two different approximate descriptions of electronic structure of molecular systems coexisted. This reproduced division of chemistry itself to organic and inorganic and took into account specificity of the molecules related to these classical fields. The organic QC was then limited by the Hiickel method, the elementary version of the HFR MO LCAO method. The description of inorganic compounds — mainly TMCs,— within the QC of that time was based on the crystal field... 

Patterns in chemical reactivity of the elements correlate with patterns in the physical structure of the atom they are both periodic functions of Z. Reading across the periodic table (horizontally) shows that each main-group element (Groups I-VIII) in Period 3 has exactly 8 more electrons than the element immediately above it in Period 2. Similarly, each main-group element in Periods 4 and 5 has exactly 18 more electrons than the corresponding element in the period above. The sequence of numbers, 8, 8, 18, 18, and so forth, that organize the periodic table into groups (columns), whose elements have similar physical and chemical properties, arises from the quantum theory of atomic structure (see discussion in Chapter 5). 

Relativistic and electron correlation effects play an important role in the electronic structure of molecules containing heavy elements (main group elements, transition metals, lanthanide and actinide complexes). It is therefore mandatory to account for them in quantum mechanical methods used in theoretical chemistry, when investigating for instance the properties of heavy atoms and molecules in their excited electronic states. In this chapter we introduce the present state-of-the-art ab initio spin-orbit configuration interaction methods for relativistic electronic structure calculations. These include the various types of relativistic effective core potentials in the scalar relativistic approximation, and several methods to treat electron correlation effects and spin-orbit coupling. We discuss a selection of recent applications on the spectroscopy of gas-phase molecules and on embedded molecules in a crystal enviromnent to outline the degree of maturity of quantum chemistry methods. This also illustrates the necessity for a strong interplay between theory and experiment. 

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