Wednesday, May 16, 2018

inorganic chemistry - Hard and Soft Acid and Bases in terms of HOMO and LUMO



It has been given in a book and on Wikipedia that:



hard bases have highest-occupied molecular orbitals (HOMO) of low energy, and hard acids have lowest-unoccupied molecular orbitals (LUMO) of high energy.[7][8]


soft bases have HOMO of higher energy than hard bases, and soft acids have LUMO of lower energy than hard acids. (However the soft-base HOMO energies are still lower than the soft-acid LUMO energies.)[7][8]



Let us consider the energy difference between HOMO and LUMO is given by $\Delta E$. Thus, $$\Delta E (S-S)<\Delta E(H-S) < \Delta E (H-H)$$


Hence the hard-hard interaction should have been weaker than hard-soft, which is not the case. Please explain.


P.S.: I went through the reference (Meissler and Tarr) and this question but could not find a satisfying explanation.




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