Density-Functional Approach to Hardness Evaluation and Its Use in the Study of the Maximum Hardness Principle

An alternative method for computing chemical hardness, based on the Janak's extension of density-functional theory for fractional occupancies, is employed in the study of the maximum hardness principle for HCN, HSiN, N2H2, HCP, and O3H+ isomerizations. The hardness is found to be a good indicat...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 120; no. 35; pp. 9053 - 9058
Main Authors Mineva, T, Sicilia, E, Russo, N
Format Journal Article
LanguageEnglish
Published American Chemical Society 09.09.1998
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Summary:An alternative method for computing chemical hardness, based on the Janak's extension of density-functional theory for fractional occupancies, is employed in the study of the maximum hardness principle for HCN, HSiN, N2H2, HCP, and O3H+ isomerizations. The hardness is found to be a good indicator of the more stable isomer in all cases. The hardnesses and the energy profiles, as a function of the reaction coordinate, are generally opposite in nature only for the isomerization reactions of O3H+ and HSiN, for which there is a negligible variation of the chemical potential. The electronic and nuclear-repulsion energy changes show good correlation with the relative stability of a species even when the constraint of constant chemical potential is not obeyed.
Bibliography:istex:7031A287C6137585F91A3E6AECBFA810CA805DC9
ark:/67375/TPS-9W5R6BLC-W
ISSN:0002-7863
1520-5126
DOI:10.1021/ja974149v