title: Observations and descriptions versus explanations--an example: does nature, does theory know about steric hindrance?
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.
authors.affiliation: TCCL, Department of Chemistry, Tsinghua University, 100084 Beijing, China. schwarz@chemie.uni-siegen.de
authors.forename: W H Eugen
authors.initials: WH
authors.lastname: Schwarz
authors.forename: Hubert
authors.initials: H
authors.lastname: Schmidbaur