engleski

Interpretation of the intrinsic molecular reactivity using triadic formula

Throughout the past decades computational chemistry has become progressively more important and has achieved full partnership with experiment as a research tool in all areas of chemistry. One of the major roles that theoretical calculations have in modern life sciences is to provide quantitative rationalization and understanding of molecular interactions and the associated interaction energy. In this work we are presenting interpretation of three elementary, but extremely important reactions in chemistry and biochemistry – protonation, deprotonation and hydride ion addition reactions in the gas-phase based on triadic paradigm. Our approach is based on the separation of the interaction process into three distinct sequential steps. Considering protonation reaction, it consists of: (1) ionization of an electron from the base (B) in question, producing radical cation, (2) attachment of the ejected electron to the incoming proton, giving the hydrogen atom and (3) creation of the chemical bond between two newly formed radicals. In the first step, initial state effect of the base is mirrored through Koopmans' approximation [IE(B)nKoop], within which the energy required to eject a particular electron equals the negative of the HOMO or any other lower-lying orbital energy. The latter is termed the principal molecular orbital and is corresponding to the lone-pair to be protonated. Relaxation energy of the radical cation (Erelax) gives intermediate stage in the protonation process, while homolytic bond association energy (BAE) reflects contribution arising from the final state effects of the protonated molecule (BH+).

triadic formula

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