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Theoretical prediction of linear free energy relationships using proton nucleomers
Author(s) -
Macchia Giovanni La,
Gagliardi Laura,
Carlson Geoffrey S.,
Jay Ashley N.,
Davis Erik,
Cramer Christopher J.
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1297
Subject(s) - chemistry , proton , value (mathematics) , free energy relationship , linear relationship , computational chemistry , thermodynamics , statistical physics , statistics , quantum mechanics , physics , kinetics , mathematics , reaction rate constant
Values of σ and σ + , for use in linear free energy relationships, are determined for para hydrogen atoms having nuclear charges other than 1 (nucleomers). Hammett ρ values for a variety of free energies of activation, reaction, and other extrathermodynamic properties (e.g., vibrational frequencies) are computed therefrom and compared to those computed using typical para functional groups. The nucleomer correlations show excellent qualitative agreement with standard correlations but the quantitative agreement is less good, typically underestimating the standard ρ ‐value by 10–60%. Copyright © 2007 John Wiley & Sons, Ltd.