Literature DB >> 22407771

Observations and descriptions versus explanations--an example: does nature, does theory know about steric hindrance?

W H Eugen Schwarz1, Hubert Schmidbaur.   

Abstract

Quantum chemical investigations in the literature sometimes underpin traditional chemical concepts (such as those of different primary and secondary types of chemical bonding or of steric repulsions) but sometimes also seem to undermine them. Conceptual pitfalls in recent discussions in this and other leading journals, when combining empirically and quantum chemically based reasoning, can be avoided when taking four points into account: 1) The construction of theoretical concepts should be guided by both, physical rigor and the aim of recovering the notions that have been found chemically fruitful. 2) Partitioning of a chemical phenomenon into elementary physical steps should not only consider the stationary initial and final states but also include non-stationary intermediate states that exhibit the physically characteristic internal relaxation mechanism. 3) Even if sufficiently accurate, the partitioning into large contributions of opposite sign is less valuable for a qualitative chemical understanding, as long as the trend of one big decisive term or sum of terms cannot be made obvious (for instance on the basis of the variation principle--or by chemical intuition). 4) Causal explanatory notions, even if more vague or fuzzy than some more rigorous and unique descriptive concepts, have to be advanced towards a more fruitful chemical theory.
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Year:  2012        PMID: 22407771     DOI: 10.1002/chem.201102687

Source DB:  PubMed          Journal:  Chemistry        ISSN: 0947-6539            Impact factor:   5.236


  1 in total

1.  On the origin of internal rotation in ammonia borane.

Authors:  Monika Parafiniuk; Mariusz P Mitoraj
Journal:  J Mol Model       Date:  2014-05-27       Impact factor: 1.810

  1 in total

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