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Acidity of first‐ and second‐row hydrides: Effects of electronegativity and hardness
Author(s) -
De Proft F.,
Langenaeker W.,
Geerlings P.
Publication year - 1995
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.560550604
Subject(s) - electronegativity , polarizability , chemistry , density functional theory , gas phase , basis set , computational chemistry , thermodynamics , molecule , organic chemistry , physics
A study is made on the influence of the electronegativity and hardness of a group X on the gas‐phase acidities of the first‐ and second‐row hydrides HX . It is shown that these two density functional theory ( DFT )‐based global properties are sufficient for the correct description of the gas‐phase acidity sequences, the group hardness being the more important factor and describing the influence of polarizability effects in the charged forms of the acid–base equilibrium. Various calculated properties of the traditional quantum chemical type (Mulliken charges and the MEP ) and DFT ‐based (local softness), associated with the neutral form of the acid, were found to contain a certain periodicity in their description of the gas‐phases acidities. The gas‐phase acidities (Δ H acid and Δ G acid values) were also obtained theoretically via quantum statistical thermodynamical calculations at the Hartree–Fock level with the 6‐31 + G* basis set; these calculated acidities were in fair agreement with the experimental ones. © 1995 John Wiley & Sons, Inc.