Title
Information theoretical study of chirality: enantiomers with one and two asymmetric centraInformation theoretical study of chirality: enantiomers with one and two asymmetric centra
Author
Faculty/Department
Faculty of Sciences. Chemistry
Research group
Structural chemistry group
Publication type
article
Publication
Washington, D.C.,
Subject
Chemistry
Source (journal)
The journal of physical chemistry : A : molecules, spectroscopy, kinetics, environment and general theory. - Washington, D.C., 1997, currens
Volume/pages
112(2008):42, p. 10560-10569
ISSN
1089-5639
1520-5215
ISI
000260100800017
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
In this work, the Kullback−Leibler information deficiency is probed as a chirality measure. It is argued that the information deficiency, calculated using the shape functions of the R and S enantiomers, considering one as reference for the other, gives an information theory based expression useful for quantifying chirality. The measure is evaluated for five chiral halomethanes possessing one asymmetric carbon atom with hydrogen, fluorine, chlorine, bromine, and iodine as substituents. To demonstrate the general applicability, a study of two halogen-substituted ethanes possessing two asymmetric carbon atoms has been included as well. The basic expression of the sum of the local information deficiency over all atoms can be decomposed into separate summations over coinciding and noncoinciding atoms, or into a global and a mixing entropy term, or into a local entropy contribution for each atom individually based on the Hirshfeld partitioning. Avnirs continuous chirality measure (CCM) has been computed and confronted with the information deficiency. Finally, the relationship between chirality and optical rotation is used to study the proposed measure. The results illustrate Mezeys holographic electron density theorem with an intuitively appealing division of the strength of propagation of the atomic chirality from an asymmetric carbon atom throughout the molecule. The local information deficiency of the carbon atom is proposed as a measure of chirality; more precisely, the difference in information between the R and the S enantiomer turns out to be a quantitative measure of the chirality of the system. It may be evaluated as the arithmetic mean of the different alignments, or considering only the alignment resulting in the highest similarity value, or using the QSSA alignment.
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