Premium
Systematic analysis of substituent effects. II. Charges and energies of atoms in fluorochloroethanes
Author(s) -
Cioslowski Jerzy,
Varnali Tereza
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)72:4<331::aid-qua16>3.0.co;2-2
Subject(s) - substituent , transferability , chemistry , charge (physics) , computational chemistry , molecule , kinetic energy , atoms in molecules , quantum , context (archaeology) , chemical physics , stereochemistry , physics , organic chemistry , quantum mechanics , statistics , mathematics , logit , paleontology , biology
Valuable insights into the nature of substituent effects are obtained by analyzing the variability of quantum mechanically defined fragment properties in terms of additive contributions. With the set of 92 fluorochloroethanes used as an example, the question of the relative importance of the direct and indirect influences of substituents upon properties of molecular fragments is addressed. The trends observed in electronic properties of entire molecules are found to originate from the additivities present at the level of individual atoms. Transferability of molecular fragments is shown to be severely compromised by the presence of significant substituent‐induced charge transfer. Contrary to some recent claims, the kinetic energies of those fragments do not correlate with the extent of charge transfer. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 331–339, 1999