Chemical reaction, acceptor-donor theory

In the third part (acceptor-donor theory of chemical reactions), we will find the answer to the question of where the reaction barrier comes from and what happens to the electronic structure when the reaction proceeds. 

As we have seen, for computational reasons we are able to take into account only reactions involving a few nuclei. However, chemists are interested in the reactivity of much larger molecules. We would like to know what particular features of the electronic structure make a chemical reaction proceed. This is the type of question that will be answered in the acceptor-donor theory. "... 

The frontier orbital theory [7-9] assumes that the stabihzation by the electron delocalization could control chemical reactions. The stabilization comes from the interactions between the occupied molecular orbitals of one molecule and the unoccupied molecular orbitals of another (Sect. 1.4). The strong interaction occurs when the energy gap is small (Sect. 1.3). The HOMO and the LUMO are the closest in energy to each other. The HOMO-LUMO interaction, especially the interaction between the HOMO of electron donors and the LUMO of electron acceptors, controls the chemical reactions (Scheme 20). The HOMO and the LUMO are termed the frontier orbitals. ... 

Molecules have some occupied and some unoccupied orbitals. There occur diverse interactions (Scheme 1) when molecules undergo reactions. According to the frontier orbital theory (Sect 3 in Chapter Elements of a Chemical Orbital Theory by Inagaki in this volume), the HOMO d) of an electron donor (D) and the LUMO (fl ) of an electron acceptor (A) play a predominant role in the chemical reactions (delocalization band in Scheme 2). The electron configuration D A where one electron transfers from dio a significantly mixes into the ground configuration DA where... 

A variety of molecular descriptors have been defined and used proceeding from frontier molecular orbital theory (FMO) of chemical reactivity [42]. This theory is based on the concept of the superdelocalizability, an index characterizing the affinity of occupied and unoccupied orbitals in chemical reactions. A distinction has been made between the electrophilic and the nucleophilic superdelocalizability (or acceptor and donor superdelocalizability), respectively. The former describes the interaction of... 

Application of the Reaction Path Hamiltonian Method to the Reaction H2 + OH —> H2O + H Acceptor-Donor (AD) Theory of Chemical Reactims (O 4)... 

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