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The role of the Frontier orbitals in acid–base chemistry of organic amines probed by ab initio and chemometric techniques
Author(s) -
La Porta Felipe A.,
Santiago Regis T.,
Ramalho Teodorico C.,
Freitas Matheus P.,
Da Cunha Elaine F. F.
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22676
Subject(s) - chemistry , molecular orbital , atomic orbital , computational chemistry , base (topology) , ab initio , quantum chemical , quantum chemistry , conjugated system , molecule , chemical physics , organic chemistry , quantum mechanics , physics , mathematical analysis , supramolecular chemistry , mathematics , polymer , electron
The Frontier effective‐for‐reaction molecular orbital (FERMO) concept emerges as a powerful and innovative implement to investigate the role of molecular orbitals (MOs) applied in the description of breakage and formation of chemical bonds. In this work, theoretical calculations were carried out for conjugated acids of 18 amines and their acid–base behavior was analyzed using MO energies. We observed that highest occupied MO (HOMO) energies are inadequate to describe the acid–base behavior of these compounds. By using the FERMO concept, the reactions that are driven by HOMO, and those that are not, can be better explained, independent of the calculation method used, as independent of the calculation method used, both HF and Kohn–Sham methodologies lead to the same FERMO. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010