Premium
Relationship between calculated core‐electron binding energy shifts and Hammett substituent (sigma) constants: I
Author(s) -
Takahata Yuji
Publication year - 2005
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.859
Subject(s) - chemistry , benzene , hammett equation , substituent , absolute deviation , sigma , density functional theory , binding energy , carbon fibers , computational chemistry , reaction rate constant , stereochemistry , organic chemistry , atomic physics , quantum mechanics , kinetics , materials science , composite number , composite material , physics , statistics , mathematics
For monosubstituted benzenes (Ph‐Z), Linderberg et al. demonstrated the validity of the equation ΔCEBE ≈ κσ, where ΔCEBE is the difference between the core‐electron binding energies (CEBE) of a specific carbon in monosubstituted benzene derivatives (Ph‐Z) and that of unsubstituted benzene (Ph‐H), κ is related to the reaction constant and σ is the experimental Hammett sigma constant. CEBEs of carbon atoms for a series of Ph‐Z were calculated using density functional theory (DFT) with the scheme Δ E KS (PW86‐PW91)/TZP+ C rel //HF/6‐31G*. An average absolute deviation of 0.15 eV was obtained with respect to observed values. A linear regression analysis of the form Y = A + BX of a plot of, for instance, Hammett σ p ‐constants against calculated ΔCEBEs (in eV) at para ‐carbon for n = 11 produced a value of A = −0.1310 and B = 1.056 with a correlation coefficient R = 0.983, a standard deviation of 0.099 and a p ‐value < 0.0001. Copyright © 2004 John Wiley & Sons, Ltd.