TY - JOUR
T1 - Theoretical prediction of linear free energy relationships using proton nucleomers
AU - La Macchia, Giovanni
AU - Gagliardi, Laura
AU - Carlson, Geoffrey S.
AU - Jay, Ashley N.
AU - Davis, Erik
AU - Cramer, Christopher J.
PY - 2008/2/1
Y1 - 2008/2/1
N2 - 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%.
AB - 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%.
KW - Computational chemistry
KW - Hammett plot
KW - Linear free energy relationship
KW - Substitution effects
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U2 - 10.1002/poc.1297
DO - 10.1002/poc.1297
M3 - Article
AN - SCOPUS:39449113048
VL - 21
SP - 136
EP - 145
JO - Journal of Physical Organic Chemistry
JF - Journal of Physical Organic Chemistry
SN - 0894-3230
IS - 2
ER -