Theoretical prediction of linear free energy relationships using proton nucleomers

Giovanni La Macchia, Laura Gagliardi, Geoffrey S. Carlson, Ashley N. Jay, Erik Davis, Christopher J. Cramer

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

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%.

Original languageEnglish (US)
Pages (from-to)136-145
Number of pages10
JournalJournal of Physical Organic Chemistry
Volume21
Issue number2
DOIs
StatePublished - Feb 1 2008

Keywords

  • Computational chemistry
  • Hammett plot
  • Linear free energy relationship
  • Substitution effects

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