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A G4 approach to computing the Hammett substituent constants σ p , σ m , σ − , σ + , and σ + m
Author(s) -
Yett Ariana,
Rablen Paul R.
Publication year - 2023
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.4436
Subject(s) - substituent , chemistry , scaling , gaussian , computational chemistry , character (mathematics) , ionic bonding , constant (computer programming) , density functional theory , hammett equation , stereochemistry , reaction rate constant , quantum mechanics , organic chemistry , mathematics , physics , geometry , ion , computer science , programming language , kinetics
By performing appropriate empirical scaling of G4 energy differences, it is possible to calculate Hammett substituent constants σ p , σ m , σ − , σ + , and σ + m with a typical accuracy (mean absolute error) of ±0.1. The procedure is straightforward and easily carried out by non‐experts using the Gaussian software package. Values are provided for 41 substituents of widely varying electronic character, including some reactive species for which experimental values are unavailable. Additionally, comparison of calculated and experimental values suggests that some previously published numbers might be significantly in error, particularly for some ionic, acidic, and/or basic substituents. Values are also provided for a newly defined substituent constant, σ − m .